Interaction between antimicrobial quaternary compounds and anionic surfactants

ABSTRACT

The invention provides activated or inactivated compositions combining quaternary ammonium compounds and anionic surfactants or acids. The invention further provides activated or inactivated compositions combining quaternary ammonium compounds and anionic chelants or polymers. Activated antimicrobial compositions comprised of a quaternary ammonium compound having less than a C20 chain length, and an anionic carboxylate surfactant having C6-C10 chain length are disclosed. Activated compositions of the invention have a pH of between about 1 and 7 and are substantially free of silanes, sulfates and oxidants. Inactivated antimicrobial compositions comprised of a quaternary ammonium compound having less than a C-20 chain length, and an anionic sulfate or sulfonate surfactant are disclosed. Compositions of the invention have a 10 mole to 1 moles ratio of quaternary ammonium compound to anionic surfactant or about 1 mole to 10 moles ratio. Methods of making and employing the compositions are disclosed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a non-provisional application claiming priority toU.S. Provisional Application No. 62/373,772, filed Aug. 11, 2016, whichis herein incorporated by reference in its entirety.

FIELD OF THE INVENTION

The present invention relates to antimicrobial compositions, includingactivated or inactivated antimicrobial compositions. In someembodiments, an antimicrobial quaternary ammonium compound is providedin combination with an anionic surfactant provide a composition havingenhanced antimicrobial properties, which may include enhanced surfaceactivity and/or sanitizing efficacy. In other aspects, an antimicrobialquaternary ammonium compound is provided in combination with an anionicpolymer or chelant. In particular, the combination provides heightenedantimicrobial activity as compared to either the anionic surfactant orthe quaternary ammonium compound alone. In other embodiments, anantimicrobial quaternary ammonium compound is provided in combinationwith an anionic surfactant to provide a composition having inactivatedantimicrobial properties. Beneficially, according to the invention anactivated or inactivated composition is provided according to aparticular application of use.

BACKGROUND OF THE INVENTION

Antimicrobial agents are chemical compositions that are used to preventmicrobiological contamination and deterioration of products, materials,mediums (such as water process streams) and systems. Antimicrobialagents and compositions are used, for example, as disinfectants orsanitizers in association with hard surface cleaning, food preparation,animal feed, cooling water, hospitality services, hospital and medicaluses, pulp and paper manufacturing, cleaning textiles, and waterprocessing. Of the diverse categories of antimicrobial agents andcompositions, quaternary ammonium compounds represent one of the largestof the classes of agents in use. At low concentrations, quaternaryammonium type antimicrobial agents are bacteriostatic, fungistatic,algistatic, sporostatic, and tuberculostatic. At medium concentrationsthey are bactericidal, fungicidal, algicidal, and viricidal againstlipophilic viruses. Quaternary ammonium compounds are known to havedifficulty in retaining kill efficacy against gram negative microbes,such as E. coli, below about 150 ppm and are also inefficient at reducedtemperatures and pH. Therefore, it is desirable to boost theantimicrobial activity of a chemical such as a quaternary ammoniumcompound. It is desirable to boost the antimicrobial activity of suchchemicals for us in various applications.

Accordingly, it is an objective of the claimed invention to develop anenhanced antimicrobial quaternary ammonium compound based composition.

It is a further object of the invention to provide a synergisticcombination of a quaternary ammonium compound and anionic surfactantproviding increased dynamic surface activity (as measured by a reductionin dynamic surface tension).

It is a further object of the invention to provide a synergisticcomposition of a quaternary ammonium compound and anionic polymers orchelants to provide such improvements and synergistic surface activity.

It is an object of the invention to provide an activated composition,having enhanced and/or synergistic surface activity, having applicationsof use including, for example, disinfectant and/or sanitizing surfaces,including high level disinfectants for medical instruments,antimicrobial lubricants, laundry cleaning and sanitizing,antimicrobials having enhanced mildness and reduced irritancy, enhancedcombination products, third sink applications, and the like.

A further object of the invention is to provide enhanced antimicrobialactivity and/or sanitizing activity with a blend of quaternary ammoniumcompound and anionic surfactant, including overcoming conventionallimitations of quaternary ammonium compounds, including conventionalrequirements for neutral to alkaline pH for performance efficacy, hardwater performance limitations requiring increased concentrations andneed for higher concentrations of actives for efficacy.

A further aspect of the invention is to provide a sanitizing compositionto improve upon the conventional quaternary ammonium compounds which arenot very surface active themselves. In an aspect, the enhancedantimicrobial activity and/or sanitizing activity with a blend ofquaternary ammonium compound and anionic surfactant, including enhancedwetting in some applications, unexpectedly provide such activity at pHneutral or above (as opposed to acidic pH conventionally employed, suchas for 500 ppm water hardness suspension tests). In a further aspect,and as a further benefit of the invention, the compositions provideenhanced mildness and reduced irritation, along with leaving lessresidue on substrate surfaces.

A further object of the invention is to provide a blend of quaternaryammonium compound and anionic surfactant capable of inactivatingantimicrobial and/or sanitizing efficacy by selection of anionicsurfactant for the composition.

It is an object of the invention to provide an inactivated compositionof the neutralized quaternary ammonium compound and anionic surfactants,having applications of use including, for example, water treatment,quaternary ammonium compound titration kits, recycling of surfactants,and the like.

Other objects, advantages and features of the present invention willbecome apparent from the following specification taken in conjunctionwith the accompanying drawings.

BRIEF SUMMARY OF THE INVENTION

The compositions according to the invention provide ability to enhanceor inactivate the antimicrobial efficacy of quaternary ammoniumcompounds. In an aspect, the selected anionic surfactants disclosedherein provide such selection for providing an antimicrobial compositionor an inactivated antimicrobial composition. According to an embodiment,anionic surfactants having strong ionic bonds serve to deactivate theantimicrobial efficacy of quaternary ammonium compounds whereas anionicsurfactants with weaker ionic bonds provide an enhanced or “activated”antimicrobial efficacy of the quaternary ammonium compounds.

Compositions of the invention provide a quaternary ammonium compound inassociation with an anionic surfactant. In some embodiments quaternaryammoniums having carbon chains of less than 20 are included incompositions of the invention. Examples of quaternary ammonium compoundsuseful in the present invention include but are not limited to alkyldimethyl benzyl ammonium chloride, alkyl dimethyl ethylbenzyl ammoniumchloride, octyl decyl dimethyl ammonium chloride, dioctyl dimethylammonium chloride, and didecyl dimethyl ammonium chloride to name a few.A single quaternary ammonium or a combination of more than onequaternary ammonium may be included in compositions of the invention.Further examples of quaternary ammonium compounds useful in the presentinvention include but are not limited to benzethonium chloride, ethylbenzethonium chloride, myristyl trimethyl ammonium chloride, methylbenzethonium chloride, cetalkonium chloride, cetrimonium bromide (CTAB),carnitine, dofanium chloride, tetraethyl ammonium bromide (TEAB),domiphen bromide, benzododecinium bromide, benzoxonium chloride,choline, cocamidopropyl betaine (CAPB), and denatonium.

Compositions of the invention further include anionic surfactants whichare selected for a desired antimicrobial or inactivated antimicrobialeffect on the quaternary ammonium compound. As described according tothe present invention, it has been found that the ability of acombination of quaternary ammonium compound and an anionic surfactantare capable to either enhance or deactivate the antimicrobial efficacywhich can be selected based upon its surface activity. That is, if acombination is highly surface active (low surface tension) as comparedto another combination, the combination having the highest surfaceactivity may enhance the antimicrobial efficacy of the quaternaryammonium. In contrast, if a combination has lower surface activity(higher surface tension) as compared to another combination, thecombination having the low surface activity neutralizes or deactivatesthe antimicrobial efficacy of the quaternary ammonium.

In certain preferred aspects, a combination of at least one quaternaryammonium compound and a carboxylate-based anionic surfactant providesimproved antimicrobial activity compared to either of the componentsused alone. In preferred aspects, the synergistic combinations increaseactivity of quaternary ammonium compounds against a microbial load whereneither the anionic surfactant nor the quaternary ammonium compound waseffective alone. Hence, the compositions set forth possess advantagesover existing antimicrobial treating agents and provide improvedresults. The combinations disclosed herein of an antimicrobial agenttogether with an anionic surfactant provide better results than wheneither of the individual components is employed separately. Examples ofpreferred carboxylate anionic surfactants for enhanced surface activityand antimicrobial efficacy of the quaternary ammonium compounds includecarboxylates having a carbon chain of C6-C10. Examples of anioniccarboxylate surfactants include organic acids such as hexanoic acid,heptanoic acid, octanoic acid, nonanoic acid, and decanoic acid.Examples of branched chain organic acids include ethylhexyl carboxylate,isononanoic acid, and tridecyl carboxylate. Examples of commerciallyavailable surfactants include Marlowet4539 (C9-alcohol polyethyleneglycol ether carboxylic acid available from Sasol). In otherembodiments, phosphate esters serve to enhance the antimicrobialactivity of a quaternary ammonium compound.

Compositions of the invention further include anionic polymer orchelant. In an aspect, the composition is a silane free quaternaryammonium compound having less than a C20 chain length and in combinationwith an anionic polymer and/or chelant. In some aspects the anionicpolymer and/or chelant used in combination with the quaternary ammoniumcompound is a polyacrylate, acrylamide, carboxylate, phosphinic acid orphosphonate salt, or mixture thereof. In an aspect, the composition hasa pH of 3 or less. In a further aspect, the composition is substantiallyfree of an oxidant. In further embodiments, the quaternary ammoniumcompound used in the compositions of the invention is comprised of amixture of dialkyl quaternary ammonium and alkyl benzyl quaternaryammonium, and the anionic polymer is a polyacrylate, acrylamide,carboxylate, phosphinic acid or phosphonate salt, or mixture thereof.

In a preferred embodiment the quaternary ammonium compound used in theantimicrobial composition of the invention is comprised of a mixture ofdialkyl quaternary ammonium and alkyl benzyl quaternary ammonium and theanionic surfactant is octanoic acid, nonanoic acid or decanoic acid or amixture thereof.

In other preferred aspects, a combination of at least one quaternaryammonium compound and a sulfate or sulfonate-based anionic surfactantprovides inactivated antimicrobial or surface activity of the quaternaryammonium compound. In certain preferred aspects, a combination of atleast one quaternary ammonium compound and an anionic surfactant thathave a stronger ionic bond deactivates the antimicrobial efficacy ofquaternary ammonium compounds. Examples of commercially availablesulfate or sulfonated anionic surfactants include X-AES(C₁₂₋₁₄-(PO)₁₆-(EO)₂-sulfate available from Huntsman Chemical), SLS(sodium lauryl sulfate), and SLES (sodium lauryl ether sulfate).

Methods of employing the compositions are also included in theembodiments of the invention.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the invention. Accordingly, the drawings anddetailed description are to be regarded as illustrative in nature andnot restrictive. These and other features, objects, and advantages, ofthe present invention will become apparent from the following detaileddescription of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot showing Dynamic Surface Tension of compositionsprepared with a 9:1 mass ratio of quaternary ammonium compound:anionicsurfactant as evaluated according to embodiments of the invention.

FIG. 2 is a plot showing Dynamic Surface Tension of compositionsprepared with a mole:mole ratio of quaternary ammonium compound: anionicsulfate surfactant.

FIG. 3A is a plot showing Dynamic Surface Tension of compositionsprepared with a mole:mole ratio of Bardac 205M quaternary ammoniumcompound:anionic carboxylate surfactants as evaluated according toembodiments of the invention.

FIG. 3B is a graphical depiction of the Dynamic Surface Tension ofBardac 205M and varying concentrations of Decanoic acid as described inExample 3.

FIG. 4A-4C depict plots comparing Dynamic Surface Tension ofcompositions prepared with quaternary ammonium compound interaction withvarious sulfate based anionic surfactants against compositions preparedwith quaternary ammonium compound with a carboxylate anionic surfactant.FIG. 4A shows evaluations with SLS. FIG. 4B shows evaluations withNAS-FAL. FIG. 4C shows evaluations with EH-S.

FIG. 5A is a plot showing the pH of compositions prepared withquaternary ammonium compound and carboxylate based anionic surfactantson a molar ratio basis as evaluated according to an embodiment of theinvention.

FIG. 5B is a plot showing the pH of compositions prepared withquaternary ammonium compound and carboxylate based anionic surfactantson a molar ratio basis as evaluated according to embodiments of theinvention.

FIG. 6A is a plot illustrating the antimicrobial efficacy ofcompositions of the invention against Escherichia coli andStaphylococcus aureus at distinct molar ratios as evaluated according toembodiments of the invention.

FIG. 6B is a plot illustrating the antimicrobial efficacy ofcompositions of the invention prepared with a quaternary ammonium:anionic surfactant ratio of 7.5:1 mass ratio with 300 ppm, 150 ppm and75 ppm Bardac 205M as evaluated according to embodiments of theinvention.

FIG. 7 is a plot showing the antimicrobial efficacy of different anionicsurfactants in combination with quaternary ammonium Bardac 205M asevaluated according to embodiments of the invention.

FIG. 8 is a plot illustrating the antimicrobial efficacy of compositionsof the invention on Staphylococcus.

FIG. 9A is a graph illustrating the antimicrobial efficacy ofcompositions of the invention on Staphylococcus at pH 4.0 or pH 8.0.

FIG. 9B is a graphical depiction the antimicrobial efficacy ofcompositions of the invention on Escherichia coli at pH 4.0 or pH 8.0.

FIG. 10 shows a graphical representation of the average dynamic surfacetension of Bardac LF80 and anionic polymers as described in Example 16.

FIG. 11 shows a graphical depiction of the average dynamic surfacetension of Bardac LF80 and varying concentrations of polymer at pH 7.0as described in Example 16.

FIG. 12 shows a graph of the average dynamic surface tension of BardacLF80 and varying concentrations of polymer at pH 11 as described inExample 16.

FIG. 13 is a graphical representation of the average dynamic surfacetension of Bardac 2250 and Anionic polymers as described in Example 17.

FIG. 14 is a graphical depiction of the average dynamic surface tensionof Bardac 2250 and varying concentrations of polymer at pH 7.0 asdescribed in Example 17.

FIG. 15 is a graph showing the average dynamic surface tension of Bardac2250 and varying concentrations of polymer at pH 11 and pH 7.0 asdescribed in Example 17.

FIG. 16 shows a graphical representation of the average dynamic surfacetension of Bardac 205M and anionic polymers as described in Example 17.

FIG. 17 shows a graphical depiction of the average dynamic surfacetension of Uniquat QAC50 and anionic polymers as described in Example17.

FIG. 18 is a graphical representation of the average dynamic surfacetension of Bardac LF80 and anionic chelant HEDP at varyingconcentrations as described in Example 18.

FIG. 19 is a graphical depiction of the average dynamic surface tensionof Bardac 2250 and anionic chelant pairs as described in Example 18.

FIG. 20 is a graph showing the average dynamic surface tension ofUniquat QAC50 and anionic chelant pairs as described in Example 18.

FIG. 21 shows a graphical representation of the average dynamic surfacetension of Bardac LF80 and anionic chelant Trilon M as a function of pHas evaluated according to embodiments of the invention.

FIG. 22 shows representative images of the removal of mineral depositsfrom polypropylene surface and chelant activation as evaluated accordingto embodiments of the invention.

FIG. 23 shows representative images of the removal of mineral depositsfrom polypropylene surface and polymer activation as evaluated accordingto embodiments of the invention.

Various embodiments of the present invention will be described in detailwith reference to the drawings, wherein like reference numeralsrepresent like parts throughout the several views. Reference to variousembodiments does not limit the scope of the invention. Figuresrepresented herein are not limitations to the various embodimentsaccording to the invention and are presented for exemplary illustrationof the invention.

DETAILED DESCRIPTION OF THE INVENTION

The embodiments of this invention are not limited to particularcompositions, methods of making and/or methods of employing the same forhard surface cleaning, including antimicrobial and/or sanitizingapplications for activated compositions, along with alternative cleaningand uses for inactivated compositions, which can vary and are understoodby skilled artisans. So that the invention may be more readilyunderstood, certain terms are first defined. It is further to beunderstood that all terminology used herein is for the purpose ofdescribing particular embodiments only, and is not intended to belimiting in any manner or scope. For example, as used in thisspecification and the appended claims, the singular forms “a,” “an” and“the” can include plural referents unless the content clearly indicatesotherwise. Further, all units, prefixes, and symbols may be denoted inits SI accepted form.

Numeric ranges recited within the specification are inclusive of thenumbers defining the range and include each integer within the definedrange. Throughout this disclosure, various aspects of this invention arepresented in a range format. It should be understood that thedescription in range format is merely for convenience and brevity andshould not be construed as an inflexible limitation on the scope of theinvention. Accordingly, the description of a range should be consideredto have specifically disclosed all the possible sub-ranges as well asindividual numerical values within that range. For example, descriptionof a range such as from 1 to 6 should be considered to have specificallydisclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numberswithin that range, for example, 1, 2, 3, 4, 5, and 6. This appliesregardless of the breadth of the range.

So that the present invention may be more readily understood, certainterms are first defined. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe invention pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used in the practice of theembodiments of the present invention without undue experimentation, thepreferred materials and methods are described herein. In describing andclaiming the embodiments of the present invention, the followingterminology will be used in accordance with the definitions set outbelow.

As used herein, the term “about” refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

The term “actives” or “percent actives” or “percent by weight actives”or “actives concentration” are used interchangeably herein and refers tothe concentration of those ingredients involved in cleaning expressed asa percentage minus inert ingredients such as water or salts.

As used herein, the term “alkyl” or “alkyl groups” refers to saturatedhydrocarbons having one or more carbon atoms, including straight-chainalkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, etc.), cyclic alkyl groups (or “cycloalkyl” or“alicyclic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups(e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), andalkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkylgroups and cycloalkyl-substituted alkyl groups).

Unless otherwise specified, the term “alkyl” includes both“unsubstituted alkyls” and “substituted alkyls.” As used herein, theterm “substituted alkyls” refers to alkyl groups having substituentsreplacing one or more hydrogens on one or more carbons of thehydrocarbon backbone. Such substituents may include, for example,alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy,alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate,alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro,trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic(including heteroaromatic) groups.

As used herein, the term “cleaning” refers to a method used tofacilitate or aid in soil removal, bleaching, microbial populationreduction, and any combination thereof. As used herein, the term“microorganism” refers to any noncellular or unicellular (includingcolonial) organism. Microorganisms include all prokaryotes.Microorganisms include bacteria (including cyanobacteria), spores,lichens, fungi, protozoa, virinos, viroids, viruses, phages, and somealgae. As used herein, the term “microbe” is synonymous withmicroorganism.

For the purpose of this patent application, successful microbialreduction is achieved when the microbial populations are reduced by atleast about 50%, or by significantly more than is achieved by a washwith water. Larger reductions in microbial population provide greaterlevels of protection.

As used herein, the term “disinfectant” refers to an agent that killsall vegetative cells including most recognized pathogenicmicroorganisms, using the procedure described in A.O.A.C. Use DilutionMethods, Official Methods of Analysis of the Association of OfficialAnalytical Chemists, paragraph 955.14 and applicable sections, 15thEdition, 1990 (EPA Guideline 91-2). As used herein, the term “high leveldisinfection” or “high level disinfectant” refers to a compound orcomposition that kills substantially all organisms, except high levelsof bacterial spores, and is effected with a chemical germicide clearedfor marketing as a sterilant by the Food and Drug Administration. Asused herein, the term “intermediate-level disinfection” or “intermediatelevel disinfectant” refers to a compound or composition that killsmycobacteria, most viruses, and bacteria with a chemical germicideregistered as a tuberculocide by the Environmental Protection Agency(EPA). As used herein, the term “low-level disinfection” or “low leveldisinfectant” refers to a compound or composition that kills someviruses and bacteria with a chemical germicide registered as a hospitaldisinfectant by the EPA.

As used herein, the phrase “food processing surface” refers to a surfaceof a tool, a machine, equipment, a structure, a building, or the likethat is employed as part of a food processing, preparation, or storageactivity. Examples of food processing surfaces include surfaces of foodprocessing or preparation equipment (e.g., slicing, canning, ortransport equipment, including flumes), of food processing wares (e.g.,utensils, dishware, wash ware, and bar glasses), and of floors, walls,or fixtures of structures in which food processing occurs. Foodprocessing surfaces are found and employed in food anti-spoilage aircirculation systems, aseptic packaging sanitizing, food refrigerationand cooler cleaners and sanitizers, ware washing sanitizing, blanchercleaning and sanitizing, food packaging materials, cutting boardadditives, third-sink sanitizing, beverage chillers and warmers, meatchilling or scalding waters, autodish sanitizers, sanitizing gels,cooling towers, food processing antimicrobial garment sprays, andnon-to-low-aqueous food preparation lubricants, oils, and rinseadditives.

As used herein, the phrase “food product” includes any food substancethat might require treatment with an antimicrobial agent or compositionand that is edible with or without further preparation. Food productsinclude meat (e.g. red meat and pork), seafood, poultry, produce (e.g.,fruits and vegetables), eggs, living eggs, egg products, ready to eatfood, wheat, seeds, roots, tubers, leafs, stems, corns, flowers,sprouts, seasonings, or a combination thereof. The term “produce” refersto food products such as fruits and vegetables and plants orplant-derived materials that are typically sold uncooked and, often,unpackaged, and that can sometimes be eaten raw.

As used herein, the phrase “health care surface” refers to a surface ofan instrument, a device, a cart, a cage, furniture, a structure, abuilding, or the like that is employed as part of a health careactivity. Examples of health care surfaces include surfaces of medicalor dental instruments, of medical or dental devices, of electronicapparatus employed for monitoring patient health, and of floors, walls,or fixtures of structures in which health care occurs. Health caresurfaces are found in hospital, surgical, infirmity, birthing, mortuary,and clinical diagnosis rooms. These surfaces can be those typified as“hard surfaces” (such as walls, floors, bed-pans, etc.), or fabricsurfaces, e.g., knit, woven, and non-woven surfaces (such as surgicalgarments, draperies, bed linens, bandages, etc.,), or patient-careequipment (such as respirators, diagnostic equipment, shunts, bodyscopes, wheel chairs, beds, etc.,), or surgical and diagnosticequipment. Health care surfaces include articles and surfaces employedin animal health care.

As used herein, the term “instrument” refers to the various medical ordental instruments or devices that can benefit from cleaning with acomposition according to the present invention.

As used herein, the phrases “medical instrument,” “dental instrument,”“medical device,” “dental device,” “medical equipment,” or “dentalequipment” refer to instruments, devices, tools, appliances, apparatus,and equipment used in medicine or dentistry. Such instruments, devices,and equipment can be cold sterilized, soaked or washed and then heatsterilized, or otherwise benefit from cleaning in a composition of thepresent invention. These various instruments, devices and equipmentinclude, but are not limited to: diagnostic instruments, trays, pans,holders, racks, forceps, scissors, shears, saws (e.g. bone saws andtheir blades), hemostats, knives, chisels, rongeurs, files, nippers,drills, drill bits, rasps, burrs, spreaders, breakers, elevators,clamps, needle holders, carriers, clips, hooks, gouges, curettes,retractors, straightener, punches, extractors, scoops, keratomes,spatulas, expressors, trocars, dilators, cages, glassware, tubing,catheters, cannulas, plugs, stents, scopes (e.g., endoscopes,stethoscopes, and arthroscopes) and related equipment, and the like, orcombinations thereof.

As used herein, the term “microbe” is synonymous with microorganism. Forthe purpose of this patent application, successful microbial reductionis achieved when the microbial populations are reduced by at least about50%, or by significantly more than is achieved by a wash with water.Larger reductions in microbial population provide greater levels ofprotection. Differentiation of antimicrobial “-cidal” or “-static”activity, the definitions which describe the degree of efficacy, and theofficial laboratory protocols for measuring this efficacy areconsiderations for understanding the relevance of antimicrobial agentsand compositions. Antimicrobial compositions can affect two kinds ofmicrobial cell damage. The first is a lethal, irreversible actionresulting in complete microbial cell destruction or incapacitation. Thesecond type of cell damage is reversible, such that if the organism isrendered free of the agent, it can again multiply. The former is termedmicrobiocidal and the later, microbiostatic. A sanitizer and adisinfectant are, by definition, agents which provide antimicrobial ormicrobiocidal activity. In contrast, a preservative is generallydescribed as an inhibitor or microbiostatic composition.

As used herein, the term “microorganism” refers to any noncellular orunicellular (including colonial) organism. Microorganisms include allprokaryotes. Microorganisms include bacteria (including cyanobacteria),spores, lichens, fungi, protozoa, virinos, viroids, viruses, phages, andsome algae.

As used herein, the term “sanitizer” refers to an agent that reduces thenumber of bacterial contaminants to safe levels as judged by publichealth requirements. In an embodiment, sanitizers for use in thisinvention will provide at least a 99.999% reduction (5-log orderreduction). These reductions can be evaluated using a procedure set outin Germicidal and Detergent Sanitizing Action of Disinfectants, OfficialMethods of Analysis of the Association of Official Analytical Chemists,paragraph 960.09 and applicable sections, 15th Edition, 1990 (EPAGuideline 91-2). According to this reference a sanitizer should providea 99.999% reduction (5-log order reduction) within 30 seconds at roomtemperature, 25±2° C., against several test organisms. According toembodiments of the invention, a sanitizing rinse provides a 99.999%reduction (5-log order reduction) of the desired organisms (includingbacterial contaminants) at a use temperature. Differentiation ofantimicrobial “-cidal” or “-static” activity, the definitions whichdescribe the degree of efficacy, and the official laboratory protocolsfor measuring this efficacy are considerations for understanding therelevance of antimicrobial agents and compositions. Antimicrobialcompositions can affect two kinds of microbial cell damage. The first isa lethal, irreversible action resulting in complete microbial celldestruction or incapacitation. The second type of cell damage isreversible, such that if the organism is rendered free of the agent, itcan again multiply. The former is termed microbiocidal and the later,microbistatic. A sanitizer and a disinfectant are, by definition, agentswhich provide antimicrobial or microbiocidal activity. In contrast, apreservative is generally described as an inhibitor or microbistaticcomposition

As used herein, the term “substantially free” refers to compositionscompletely lacking the component or having such a small amount of thecomponent that the component does not affect the performance of thecomposition. The component may be present as an impurity or as acontaminant and shall be less than 0.5 wt-%. In another embodiment, theamount of the component is less than 0.1 wt-% and in yet anotherembodiment, the amount of component is less than 0.01 wt-%.

The term “surfactant” as used herein is a compound that contains alipophilic segment and a hydrophilic segment, which when added to wateror solvents, reduces the surface tension of the system.

As used herein, the term “ware” refers to items such as eating andcooking utensils, dishes, and other hard surfaces such as showers,sinks, toilets, bathtubs, countertops, windows, mirrors, transportationvehicles, and floors. As used herein, the term “warewashing” refers towashing, cleaning, or rinsing ware. Ware also refers to items made ofplastic. Types of plastics that can be cleaned with the compositionsaccording to the invention include but are not limited to, those thatinclude polycarbonate polymers (PC), acrilonitrile-butadiene-styrenepolymers (ABS), and polysulfone polymers (PS). Another exemplary plasticthat can be cleaned using the compounds and compositions of theinvention include polyethylene terephthalate (PET).

As used herein, the term “waters” includes food process or transportwaters. Food process or transport waters include produce transportwaters (e.g., as found in flumes, pipe transports, cutters, slicers,blanchers, retort systems, washers, and the like), belt sprays for foodtransport lines, boot and hand-wash dip-pans, third-sink rinse waters,and the like. Waters also include domestic and recreational waters suchas pools, spas, recreational flumes and water slides, fountains, and thelike.

As used herein, “weight percent,” “wt-%,” “percent by weight,” “% byweight,” and variations thereof refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

As used herein, the term “water soluble” refers to a composition or acomponent if it is at least 90 percent soluble in water, at least 95percent soluble in water, at least 98 percent soluble in water, at least99 percent soluble in water, or at least 99.9 percent soluble in water.

The methods and compositions of the present invention may comprise,consist essentially of, or consist of the components and ingredients ofthe present invention as well as other ingredients described herein. Asused herein, “consisting essentially of” means that the methods andcompositions may include additional steps, components or ingredients,but only if the additional steps, components or ingredients do notmaterially alter the basic and novel characteristics of the claimedmethods and compositions.

Activated Antimicrobial Compositions

According to the invention, the antimicrobial compositions combining atleast one quaternary ammonium compound and at least one anionicsurfactant provide improved antimicrobial activity than either of thecomponents used alone. In some aspects, the antimicrobial compositionsaccording to the invention beneficially provide synergistic surfaceactivity (reduced dynamic surface tension) and are cost effective. Ithas further been discovered that combinations of synergisticantimicrobial and/or sanitizing efficacy also serve to reduce theunpleasant smell of certain anionic surfactants (e.g. C6-C10carboxylated surfactants), such as fatty acids, providing a stillfurther benefit of the compositions of the invention.

In an aspect, the antimicrobial compositions according to the inventioncomprise, consist of and/or consist essentially of a quaternary ammoniumcompound and an anionic surfactant and/or anionic acid. In anotheraspect, the antimicrobial compositions according to the inventioncomprise, consist of and/or consist essentially of a quaternary ammoniumcompound having each R group with a C20 or less chain length, and ananionic surfactant having a C10 or less chain length for linear orbranched carboxylates. In an aspect the carboxylates may be alkoxylatedor unalkoxylated. In another aspect, the antimicrobial compositionsaccording to the invention comprise, consist of and/or consistessentially of a quaternary ammonium compound having each R group with aC20 or less chain length, and an anionic surfactant having a C13 or lesschain length for alkoxylated anionic linear or branched carboxylates.

The antimicrobial compositions according to the invention overcome theinsufficient surface activity of the quaternary ammonium compounds whileproviding efficacious antimicrobial and/or sanitizing capabilities. Thecompositions of quaternary ammonium compound and anionic surfactantbecome synergistically more surface active and efficacious, whichbeneficially provide improved performance under stressed conditions. Insome aspects, the antimicrobial compositions are efficacious at neutraland/or alkaline pH (as opposed to lower pH range of about 1-5 requiredfor EPA standards used in water hardness suspension testing).Beneficially, the selection of the anionic surfactant and quaternaryammonium compound activate (i.e. cause synergy) the quaternary ammoniumcompound to provide desired surface activity, including antimicrobialand/or sanitizing activity, as a result of the synergy and improvedwettability of the compositions. In an aspect, and without being limitedto a particular mechanism of action, the anionic surfactant having a C10or less chain length provides the activation suitable for providing anantimicrobial composition according to the invention. This combinationof quaternary ammonium compound and anionic surfactant having a desiredanionic head group and chain length is a non-oxidative approach toenhancing the surface activity of and the antimicrobial efficacy of thequaternary ammonium compound complex in an unexpected manner. Moreover,the antimicrobial compositions provided have an enhanced mildness andreduced irritancy as a result of the neutralization or partialneutralization, as well as result in reduced residue on substratesurfaces.

According to some embodiments, the antimicrobial compositions accordingto the invention provide surface activation and synergy of thequaternary ammonium compound that are molar ratio dependent. In anaspect, the compositions include approximately a mole to mole ratio ofquaternary ammonium compound and anionic surfactant. In other aspects,the compositions include up to about a 10 to about a 1 molar ratio ofquaternary ammonium compound and anionic surfactant. In other aspects,the compositions include up to about 1 to about a 10 molar ratio ofquaternary ammonium compound and anionic surfactant, or any combinationthereof. In another embodiment the antimicrobial compositions areprovided with a molar ratio of anionic surfactant to quaternary ammoniumof about 1 mole anionic surfactant to about 1 mole of quaternaryammonium compound. In another embodiment the antimicrobial compositionis provided with a molar ratio of anionic surfactant to quaternaryammonium compound of about 1.5 mole anionic surfactant to about 1 moleof quaternary ammonium compound. In another embodiment the antimicrobialcomposition is provided with a molar ratio of anionic surfactant toquaternary ammonium compound of about 1 mole anionic surfactant to about10 moles of quaternary ammonium compound. In another embodiment theantimicrobial composition is provided with a molar ratio of anionicsurfactant to quaternary ammonium compound of about 2 moles anionicsurfactant to about 1 mole of quaternary ammonium compound.

Inactivated Antimicrobial Compositions (Inactivation of AntimicrobialQACs)

It has further been discovered that modifications to the antimicrobialcompositions described herein can be made to preferentially select theat least one quaternary ammonium compound and at least one anionicsurfactant to provide an inactivated composition. According to theinvention, some anionic surfactants work to decrease the antimicrobialactivity of the quaternary ammonium compound. In an aspect, sulfated andsulfonated anionic surfactants inactivate the antimicrobial activity ofquaternary ammonium compounds. It is believed that anionic surfactantswith a stronger ionic charge serve to deactivate the antimicrobialefficacy of quaternary ammonium compounds whereas anionic surfactantswith a weaker ionic charge serve to enhance or activate theantimicrobial efficacy of quaternary ammonium compounds.

In an aspect, the inactivated antimicrobial compositions according tothe invention comprise, consist of and/or consist essentially of aquaternary ammonium compound and an anionic surfactant. In anotheraspect, the inactivated antimicrobial compositions according to theinvention comprise, consist of and/or consist essentially of aquaternary ammonium compound having each R group with a C20 or lesschain length, and a sulfate or sulfonate anionic surfactant having analkyl chain greater than C10 for linear or branched.

The inactivated antimicrobial compositions according to the inventiondesirably provide decreased surface activity of the quaternary ammoniumcompound for particular applications of use. Without being bound bytheory, the present invention demonstrates that a complex, or ion pair,between a quat and anionic surfactant, because of the chargeneutralization, effectively reduces the hydrophilic cross-sectionalareas for both surfactants, making stacking in interfaces veryfavorable. The complex formation is so favorable that it can overcomethe cohesive force between fatty acid molecules. According to an aspectof the invention, stronger ionic charge with certain anionicsurfactants, such as sulfate or sulfonate anionic surfactants,effectively neutralizes (or partially neutralizes the quaternaryammonium ionic charge) or inactivates the antimicrobial quaternaryammonium compound.

According to some embodiments, the inactivated antimicrobialcompositions according to the invention provide decrease surfaceactivation of the quaternary ammonium compound that are molar ratiodependent. In an aspect, the compositions include approximately a moleto mole ratio of quaternary ammonium compound and anionic surfactant. Inother aspects, the compositions include up to about a 10 to about a 1molar ratio of quaternary ammonium compound and anionic surfactant. Inother aspects, the compositions include up to about a 1 to about a 10molar ratio of quaternary ammonium compound and anionic surfactant. Inanother embodiment the inactivated antimicrobial compositions areprovided with a molar ratio of anionic surfactant to quaternary ammoniumof about 1 mole anionic surfactant to about 1 mole of quaternaryammonium compound. In another embodiment the inactivated antimicrobialcomposition is provided with a molar ratio of anionic surfactant toquaternary ammonium compound of about 1.5 mole anionic surfactant toabout 1 mole of quaternary ammonium compound. In another embodiment theinactivated antimicrobial composition is provided with a molar ratio ofanionic surfactant to quaternary ammonium compound of about 1 moleanionic surfactant to about 10 moles of quaternary ammonium compound. Inanother embodiment the inactivated antimicrobial composition is providedwith a molar ratio of anionic surfactant to quaternary ammonium compoundof about 2 moles anionic surfactant to about 1 mole of quaternaryammonium compound.

Exemplary Embodiments

Exemplary ranges of the activated or inactivated antimicrobialcompositions according to the invention in concentrated liquidcompositions are shown in Table 1 each in weight percentage.

TABLE 1 First Second Third Exemplary Exemplary Exemplary Material Rangewt-% Range wt-% Range wt-% Quaternary ammonium 0.001-75 1-50 1-30compound Anionic surfactant or 0.0001-50  0.1-30   0.1-20   polymer orchelant Additional Functional   0-90 0-75 0-50 Ingredients

According to the invention, the concentrated antimicrobial compositionsand/or inactivated antimicrobial compositions set forth in Table 1 haveany suitable pH for applications of use, including from about 1 to about12. However, according to aspects of the invention, the diluted usesolutions may have acidic or neutral to alkaline pH depending upon aparticular application of use thereof, including form about 1 to about12.

In some aspects, such as applications of a use solution of theantimicrobial compositions and/or inactivated antimicrobial compositionsmay have a pH from about 1 to about 12. In other aspects, thecompositions of the invention have a pH between about 1 and about 7. Inother aspects, the compositions of the invention have a pH between about1 and about 5.5. In still other aspects, the compositions of theinvention have a pH between about 1 and about 4. In another embodimentthe composition has a pH between about 2 and about 7, between about 3and about 7, between about 4 and about 7, between about 5 and about 7,between about 6 and about 7. In another embodiment the composition has apH between about 1 and about 6, between about 1 and about 5, betweenabout 1 and about 4, between about 1 and about 3, between about 1 andabout 2. In yet other embodiments the composition has a pH between about2 and about 6, between about 3 and about 6, between about 4 and about 6,between about 5 and about 6. In yet other embodiments the compositionhas a pH between about 1 and about 5, between about 2 and about 5,between about 3 and about 5, between about 4 and about 5. In yet otherembodiments the composition has a pH between about 1 and about 4,between about 2 and about 4, between about 3 and about 4. Withoutlimiting the scope of invention, the numeric ranges are inclusive of thenumbers defining the range and include each integer within the definedrange.

Quaternary Ammonium Compound

The antimicrobial compositions and inactivated antimicrobialcompositions according to the invention include at least one quaternaryammonium compound. Certain quaternary ammonium compounds are known tohave antimicrobial activity. Accordingly, various quaternary ammoniumcompound with antimicrobial activity can be used in the composition ofthe invention. In an aspect, the quaternary ammonium compound is anantimicrobial “quat.” The term “quaternary ammonium compound” or “quat”generally refers to any composition with the following formula:

where R1-R4 are alkyl groups that may be alike or different, substitutedor unsubstituted, saturated or unsaturated, branched or unbranched, andcyclic or acyclic and may contain ether, ester, or amide linkages; theymay be aromatic or substituted aromatic groups. In an aspect, groups R1,R2, R3, and R4 each have less than a C20 chain length. X— is an anioniccounterion. The term “anionic counterion” includes any ion that can forma salt with quaternary ammonium. Examples of suitable counterionsinclude halides such as chlorides and bromides, propionates,methosulphates, saccharinates, ethosulphates, hydroxides, acetates,phosphates, carbonates (such as commercially available as Carboquat H,from Lonza), and nitrates. Preferably, the anionic counterion ischloride.

Compositions of the invention provide a quaternary ammonium compound inassociation with an anionic surfactant. In some embodiments quaternaryammoniums having carbon chains of less than 20 are included incompositions of the invention. Examples of quaternary ammonium compoundsuseful in the present invention include but are not limited to alkyldimethyl benzyl ammonium chloride, alkyl dimethyl ethylbenzyl ammoniumchloride, octyl decyl dimethyl ammonium chloride, dioctyl dimethylammonium chloride, and didecyl dimethyl ammonium chloride to name a few.A single quaternary ammonium or a combination of more than onequaternary ammonium may be included in compositions of the invention.Further examples of quaternary ammonium compounds useful in the presentinvention include but are not limited to benzethonium chloride, ethylbenzethonium chloride, myristyl trimethyl ammonium chloride, methylbenzethonium chloride, cetalkonium chloride, cetrimonium bromide (CTAB),carnitine, dofanium chloride, tetraethyl ammonium bromide (TEAB),domiphen bromide, benzododecinium bromide, benzoxonium chloride,choline, cocamidopropyl betaine (CAPB), and denatonium.

In some embodiments quaternary ammoniums having carbon chains of lessthan 20 or C2-C20 are included in compositions of the invention. Inother embodiments quaternary ammoniums having carbon chains of C6-C18,C12-C18, C12-C16 and C6-C10 are included in compositions of theinvention. Examples of quaternary ammonium compounds useful in thepresent invention include but are not limited to alkyl dimethyl benzylammonium chloride, alkyl dimethyl ethylbenzyl ammonium chloride, octyldecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride,and didecyl dimethyl ammonium chloride to name a few. A singlequaternary ammonium or a combination of more than one quaternaryammonium may be included in compositions of the invention. Furtherexamples of quaternary ammonium compounds useful in the presentinvention include but are not limited to benzethonium chloride,ethylbenzyl alkonium chloride, myristyl trimethyl ammonium chloride,methyl benzethonium chloride, cetalkonium chloride, cetrimonium bromide(CTAB), carnitine, dofanium chloride, tetraethyl ammonium bromide(TEAB), domiphen bromide, benzododecinium bromide, benzoxonium chloride,choline, cocamidopropyl betaine (CAPB), denatonium, and mixturesthereof. In an aspect, combinations of quaternary ammonium compounds areparticularly preferred for compositions of the invention, such as forexample the commercially-available products Bardac 205/208M.

In some embodiments depending on the nature of the R group, the anion,and the number of quaternary nitrogen atoms present, the antimicrobialquaternary ammonium compounds may be classified into one of thefollowing categories: monoalkyltrimethyl ammonium salts;monoalkyldimethylbenzyl ammonium salts; dialkyldimethyl ammonium salts;heteroaromatic ammonium salts; polysubstituted quaternary ammoniumsalts; bis-quaternary ammonium salts; and polymeric quaternary ammoniumsalts. Each category will be discussed herein.

Monoalkyltrimethyl ammonium salts contain one R group that is along-chain alkyl group, and the remaining R groups are short-chain alkylgroups, such as methyl or ethyl groups. Some non-limiting examples ofmonoalkyltrimethyl ammonium salts include cetyltrimethylammoniumbromide, commercial available under the tradenames Rhodaquat M242C/29and Dehyquart A; alkyltrimethyl ammonium chloride, commerciallyavailable as Arquad 16; alkylaryltrimethyl ammonium chloride; andcetyldimethyl ethylammonium bromide, commercially available as AmmonyxDME.

Monoalkyldimethylbenzyl ammonium salts contain one R group that is along-chain alkyl group, a second R group that is a benzyl radical, andthe two remaining R groups are short-chain alkyl groups, such as methylor ethyl groups. Monoalkyldimethylbenzyl ammonium salts are generallycompatible with nonionic surfactants, detergent builders, perfumes, andother ingredients. Some non-limiting examples of monoalkyldimethylbenzylammonium salts include alkyldimethylbenzyl ammonium chlorides,commercially available as Barquat from Lonza Inc.; and benzethoniumchloride, commercially available as Lonzagard, from Lonza Inc.Additionally, the monoalkyldimethylbenzyl ammonium salts may besubstituted. Non-limiting examples of such salts includedodecyldimethyl-3,4-dichlorobenzyl ammonium chloride. Finally, there aremixtures of alkyldimethylbenzyl and alkyldimethyl substituted benzyl(ethylbenzyl) ammonium chlorides commercially available as BTC 2125Mfrom Stepan Company, and Barquat 4250 from Lonza Inc.

Dialkyldimethyl ammonium salts contain two R groups that are long-chainalkyl groups, and the remaining R groups are short-chain alkyl groups,such as methyl groups. Some non-limiting examples of dialkyldimethylammonium salts include didecyldimethyl ammonium halides, commerciallyavailable as Bardac 22 from Lonza Inc.; didecyl dimethyl ammoniumchloride commercially available as Bardac 2250 from Lonza Inc.; dioctyldimethyl ammonium chloride, commercially available as Bardac LF andBardac LF-80 from Lonza Inc.); and octyl decyl dimethyl ammoniumchloride sold as a mixture with didecyl and dioctyl dimethyl ammoniumchlorides, commercially available as Bardac2050 and 2080 from Lonza Inc.

Heteroaromatic ammonium salts contain one R group that is a long-chainalkyl group, and the remaining R groups are provided by some aromaticsystem. Accordingly, the quaternary nitrogen to which the R groups areattached is part of an aromatic system such as pyridine, quinoline, orisoquinoline. Some non-limiting examples of heteroaromatic ammoniumsalts include cetylpyridinium halide, commercially available as Sumquat6060/CPC from Zeeland Chemical Inc.;1-[3-chloroalkyl]-3,5,7-triaza-1-azoniaadamantane, commerciallyavailable as Dowicil 200 from The Dow Chemical Company; andalkyl-isoquinolinium bromide.

Polysubstituted quaternary ammonium salts are a monoalkyltrimethylammonium salt, monoalkyldimethylbenzyl ammonium salt, dialkyldimethylammonium salt, or heteroaromatic ammonium salt wherein the anion portionof the molecule is a large, high-molecular weight (MW) organic ion. Somenon-limiting examples of polysubstituted quaternary ammonium saltsinclude alkyldimethyl benzyl ammonium saccharinate, anddimethylethylbenzyl ammonium cyclohexylsulfamate.

Bis-quatemary ammonium salts contain two symmetric quaternary ammoniummoieties having the general formula:

Where the R groups may be long or short chain alkyl, a benzyl radical orprovided by an aromatic system. Z is a carbon-hydrogen chain attached toeach quaternary nitrogen. Some non-limiting examples of bis-quaternaryammonium salts include 1,10-bis(2-methyl-4-aminoquinoliniumchloride)-decane; and 1,6-bis[1-methyl-3-(2,2,6-trimethylcyclohexyl)-propyldimethylammonium chloride] hexane or triclobisoniumchloride.

In an aspect, the quaternary ammonium compound is a medium to long chainalkyl R group, such as from 8 carbons to about 20 carbons, from 8carbons to about 18 carbons, from about 10 to about 18 carbons, and fromabout 12 to about 16 carbons, and providing a soluble and goodantimicrobial agent.

In an aspect, the quaternary ammonium compound is a short di-alkyl chainquaternary ammonium compound having an R group, such as from 2 carbonsto about 12 carbons, from 3 carbons to about 12 carbons, or from 6carbons to about 12 carbons.

In a preferred aspect, the quaternary ammonium compound is an alkylbenzyl ammonium chloride, a dialkyl benzyl ammonium chloride, a blend ofalkyl benzyl ammonium chloride and dialkyl benzyl ammonium chloride,didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride,a blend of didecyl dimethyl ammonium chloride and dioctyl dimethylammonium chloride, or mixtures thereof. In a preferred embodiment thequaternary ammonium compound used in the antimicrobial compositions ofthe invention is comprised of a mixture of dialkyl quaternary ammoniumand alkyl benzyl quaternary ammonium.

In some embodiments, the quaternary ammonium compound is silane free. Inpreferred embodiments, the antimicrobial composition is providedincluding a silane free quaternary ammonium compound having less than aC-20 chain length.

In a preferred embodiment, the quaternary ammonium compound may beselected based on its consideration or classification as a foodadditive. For example, the quaternary ammonium compound may includebenzalkonium chloride and is therefore suitable for use in a sanitizingrinse for contact with food products.

According to embodiments of the invention providing antimicrobialcompositions, an effective amount of the quaternary ammonium compound isprovided in combination with the anionic surfactant to providesynergistic antimicrobial efficacy against a broad spectrum of microbes,including gram negative microbes such as E. coli. Suitableconcentrations of the quaternary ammonium compound in such a usesolution include at least about 10 ppm, at least about 50 ppm, or atleast about 100 ppm, or at least about 150 ppm, or at least about 200ppm, or at least about 250 ppm, or at least about 300 ppm, or from about100-500 ppm, or from about 100-300 ppm, or any ranges therein. In someaspects, the activated microbial compositions according to the inventionprovide efficacy against gram negative conventionally requirement morethan 150 ppm quaternary ammonium compounds for any antimicrobialefficacy at concentrations below about 150 ppm, or below about 100 ppmaccording to the synergy in combination with the anionic surfactantsand/or acids. Beneficially, the low actives of the quaternary ammoniumcompound is a result of the beneficial synergy with the anionicsurfactant. Without being limited according to the invention, all rangesrecited are inclusive of the numbers defining the range and include eachinteger within the defined range.

According to embodiments of the invention providing inactivatedantimicrobial compositions, an effective amount of the quaternaryammonium compound is provided in combination with the anionic surfactantto provide an inactivated quaternary ammonium composition, such as maybe desired not impact the antimicrobial efficacy of a treated system.Suitable concentrations of the quaternary ammonium compound in such ause solution include at least about 0.0001 ppm, at least about 0.001ppm, or at least about 0.01 ppm, or any ranges therein, or any suitablemolar concentration of the inactivating anionic to the quaternaryammonium compound concentration for a particular application of use.Without being limited according to the invention, all ranges recited areinclusive of the numbers defining the range and include each integerwithin the defined range.

Additional suitable concentrations of the quaternary ammonium compoundin a use solution for the antimicrobial compositions and inactivatedantimicrobial compositions include between about 1 ppm and about 10,000ppm, 1 ppm and about 1,000 ppm, 5 ppm and about 400 ppm, 10 ppm andabout 400 ppm, 20 ppm and about 400 ppm, 25 ppm and about 400 ppm, 50ppm and about 400 ppm, 75 ppm and about 400 ppm, or 100 ppm and about400 ppm. Without being limited according to the invention, all rangesrecited are inclusive of the numbers defining the range and include eachinteger within the defined range.

According to embodiments of the invention, the quaternary ammoniumcompound may be provided in a concentrated composition in the amountbetween about 0.001 wt.-%-75 wt.-%, from about 0.1 wt.-%-75 wt.-%, fromabout 0.01 wt.-%-75 wt.-%, from about 1 wt.-%-75 wt.-%, from about 1wt.-%-50 wt.-%, from about 1 wt.-%-30 wt.-%, from about 5 wt.-%-30wt.-%. In addition, without being limited according to the invention,all ranges recited are inclusive of the numbers defining the range andinclude each integer within the defined range.

Anionic Surfactants

The antimicrobial compositions and/or inactivated antimicrobialcompositions according to the invention include at least one anionicsurfactant. In other aspects, the antimicrobial compositions and/orinactivated antimicrobial compositions according to the inventioninclude at least two anionic surfactants. Anionic surfactants arecategorized as anionics because the charge on the hydrophile isnegative; or surfactants in which the hydrophilic section of themolecule carries no charge unless the pH is elevated to pKa orneutrality or above (e.g. carboxylic acids). Carboxylate, sulfonate,sulfate and phosphate are polar (hydrophilic) solubilizing groups foundin anionic surfactants.

In an aspect, the anionic surfactant is linear or branched. In anaspect, the linear or branched anionic surfactant is a medium chainsurfactant having from 6-20 carbon chain length, or from 6-18 carbonchain length, preferably from 6-12 carbon chain length, and morepreferably from 6-10 carbon chain length. In an aspect, the linear orbranched, medium chain anionic surfactant is alkoxylated. In an aspect,the linear or branched anionic surfactant is an alkoxylated medium chainsurfactant having from 6-18 carbon chain length, preferably from 6-13carbon chain length, and more preferably from 6-10 carbon. In an aspect,the anionic surfactant is a carboxylate. In an alternative aspect, theanionic surfactant is a weak acid anionic, such as a phosphate ester. Ina still further alternative aspect, the anionic surfactant is asulfonate and/or sulfate. In still further aspect, the anionicsurfactant used in combination with the quaternary ammonium isalkoxylated or un-alkoxylated and may be a primary linear chain orbranched chain carboxylate.

In an aspect, the anionic surfactant suitable for use in the presentcompositions to activate the synergy and enhanced surface activity ofthe quaternary ammonium compound include carboxylates. Anioniccarboxylate surfactants suitable for use in the present compositionsinclude carboxylic acids (and salts), such as alkanoic acids (andalkanoates), ester carboxylic acids (e.g. alkyl succinates), ethercarboxylic acids, sulfonated fatty acids, such as sulfonated oleic acid,and the like Suitable carboxylic acids include for example decanoicacid, octanoic acid, nonanoic, ethylhexyl acid, and isononanionic acid.Such carboxylates include alkyl ethoxy carboxylates, alkyl aryl ethoxycarboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps(e.g. alkyl carboxyls). Secondary carboxylates useful in the presentcompositions include those which contain a carboxyl unit connected to asecondary carbon. The secondary carbon can be in a ring structure, e.g.as in p-octyl benzoic acid, or as in alkyl-substituted cyclohexylcarboxylates. The secondary carboxylate surfactants typically contain noether linkages, no ester linkages and no hydroxyl groups. Further, theytypically lack nitrogen atoms in the head-group (amphiphilic portion).Suitable secondary soap surfactants typically contain 11-13 total carbonatoms, although more carbons atoms (e.g., up to 16) can be present.Suitable carboxylates also include acylamino acids (and salts), such asacylgluamates, acyl peptides, sarcosinates (e.g. N-acyl sarcosinates),taurates (e.g. N-acyl taurates and fatty acid amides of methyl tauride),and the like.

Suitable anionic surfactants include alkyl or alkylaryl ethoxycarboxylates of the following formula: R—O—(CH₂CH₂O)_(n)(CH₂)_(m)—CO₂Xin which R is a C8-C22 alkyl group or

in which R1 is a C4-C16 alkyl group; n is an integer of 1-20; m is aninteger of 1-3; and X is a counter ion, such as hydrogen, sodium,potassium, lithium, ammonium, or an amine salt such as monoethanolamine,diethanolamine or triethanolamine. In some embodiments, n is an integerof 4 to 10 and m is 1. In some embodiments, R is a C8-C16 alkyl group.In some embodiments, R is a C12-C14 alkyl group, n is 4, and m is 1.

Such alkyl and alkylaryl ethoxy carboxylates are commercially available.These ethoxy carboxylates are typically available as the acid forms,which can be readily converted to the anionic or salt form.

In an aspect, the carboxylate-based anionic surfactant provides improvedantimicrobial activity than either of the components used alone.Examples of preferred activating anionic surfactants includecarboxylates having a carbon chain of C6-C10. Examples of anioniccarboxylate surfactants include organic acids such as hexanoic acid,heptanoic acid, octanoic acid, nonanoic acid, and decanoic acid.Examples of branched chain organic acids include ethylhexyl carboxylateand tridecyl carboxylate. Examples of commercially available surfactantsinclude Marlowet 4539 (C9-alcohol polyethylene glycol ether carboxylicacid available from Sasol), Emulsogen CNO (C8-alcohol 8 molespolyethylene glycol ether carboxylic acid available from Clariant), andEmulsogen DTC (C13-alcohol 7 moles polyethylene glycol ether carboxylicacid available from Clariant), and others.

In an aspect, the anionic surfactant suitable for use in the presentcompositions to activate the microbial synergy and enhanced surfaceactivity (as measured by a reduction in dynamic surface tension) of thequaternary ammonium compound further include phosphate esters.

In an aspect, the anionic surfactant suitable for use in the presentcompositions to inactivate or decrease the surface activity of thequaternary ammonium compound include sulfonates and/or sulfates. In anaspect, the anionic surfactant suitable for use in the presentcompositions include alkyl ether sulfates, alkyl sulfates, the linearand branched primary and secondary alkyl sulfates, alkyl ethoxysulfates,fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ethersulfates, the C5-C17 acyl-N—(C1-C4 alkyl) and —N—(C1-C2 hydroxyalkyl)glucamine sulfates, and sulfates of alkylpolysaccharides such as thesulfates of alkylpolyglucoside, and the like. Also included are thealkyl sulfates, alkyl poly(ethyleneoxy) ether sulfates and aromaticpoly(ethyleneoxy) sulfates such as the sulfates or condensation productsof ethylene oxide and nonyl phenol (usually having 1 to 6 oxyethylenegroups per molecule). Anionic sulfonate surfactants suitable for use inthe present compositions also include alkyl sulfonates, the linear andbranched primary and secondary alkyl sulfonates, and the aromaticsulfonates with or without sub stituents.

In an aspect, the sulfated and sulfonated anionic surfactants providedecreased or inactivated surface activity of the quaternary ammoniumcompound. Sulfated and sulfonated anionic surfactants have a strongerionic bond serve to deactivate the antimicrobial efficacy of quaternaryammonium compounds whereas anionic surfactants with weaker ionic bondsserve to enhance or activate the antimicrobial efficacy of quaternaryammonium compounds. Examples of commercially available sulfate orsulfonated anionic surfactants include X-AES(C₁₂₋₁₄-(PO)₁₆-(EO)₂-sulfate available from Huntsman Chemical), SLS(sodium lauryl sulfate), SLES (sodium lauryl ether sulfate), LAS (linearalkyl benzyl sulfonate), and AOS (alpha olefin sulfonate).

As described herein according to the invention, the ability of acombination of quaternary ammonium compound and an anionic surfactant toeither enhance or deactivate the antimicrobial efficacy can be predictedbased upon its surface activity. That is, if a combination is highlysurface active as compared to another combination (which indicates thequaternary ammonium compound is water soluble and therefore availablefor surface activity and antimicrobial action), the combination havingthe highest surface activity enhances the antimicrobial efficacy of thequaternary ammonium. In contrast, if a combination has lower surfaceactivity as compared to another combination, the combination having thelow surface activity neutralizes or deactivates the antimicrobialefficacy of the quaternary ammonium.

In an aspect of the invention, the antimicrobial efficacy of acomposition may be dialed up or down depending upon the anionicsurfactant employed. According to the invention, a method of modulatingantimicrobial activity of a quaternary ammonium compound is provided.

According to embodiments of the invention providing antimicrobialcompositions, an effective amount of the anionic surfactant is providedin combination with the quaternary ammonium compound to providesynergistic antimicrobial efficacy. Suitable concentrations of theanionic surfactant in a use solution include between about 1 ppm andabout 5,000 ppm, about 15 ppm and about 2,500 ppm, about 1 ppm and about1,000 ppm, about 1 ppm and about 100 ppm, about 1 ppm and about 50 ppm,or about 1 ppm and about 5 ppm. Without being limited according to theinvention, all ranges recited are inclusive of the numbers defining therange and include each integer within the defined range.

According to other embodiments of the invention providing inactivatedantimicrobial compositions, an effective amount of the anionicsurfactant is provided in combination with the quaternary ammoniumcompound to inactivate or decrease antimicrobial efficacy of thequaternary ammonium compound. Suitable concentrations of the anionicsurfactant in a use solution include between about 1 ppm and about 5,000ppm, about 15 ppm and about 2,500 ppm, about 1 ppm and about 1,000 ppm,about 1 ppm and about 100 ppm, about 1 ppm and about 50 ppm, or about 1ppm and about 25 ppm.

According to embodiments of the invention, the anionic surfactant may beprovided in a concentrated composition in the amount between about0.0001 wt.-%-50 wt.-%, from about 0.001 wt.-%-50 wt.-%, from about 0.01wt.-%-50 wt.-%, from about 0.1 wt.-%-50 wt.-%, from about 0.1 wt.-%-30wt.-%, from about 1 wt.-%-30 wt.-%, from about 0.1 wt.-%-20 wt.-%, orfrom about 1 wt.-%-20 wt.-%. In addition, without being limitedaccording to the invention, all ranges recited are inclusive of thenumbers defining the range and include each integer within the definedrange. As one skilled in the art will ascertain from the disclosure ofthe present invention, the concentrations for the anionic surfactantand/or acid in combination with the quaternary ammonium compound willvary dependent upon the type of anionic surfactant (e.g. selected foractivation versus inactivation), quaternary ammonium compoundconcentration (molar ratio) and the additional components in thesolution of the composition.

Anionic Polymers and/or Chelants

In some embodiments, the compositions according to the invention includeat least one anionic polymer or chelant in combination with thequaternary ammonium compound to provide the surface active complex. Inother aspects, the compositions according to the invention include atleast two anionic polymers, or an anionic polymer and an anionicsurfactant. In other aspects, the compositions according to theinvention include at least two anionic chelants, or an anionic polymerand an anionic chelant, or an anionic chelant and an anionic surfactant.Anionic polymers and chelants are categorized as anionics because thecharge on the hydrophobe is negative; or surfactants in which thehydrophobic section of the molecule carries no charge unless the pH iselevated to neutrality or above (e.g. carboxylic acids). Carboxylate,sulfonate, sulfate and phosphate are polar (hydrophilic) solubilizinggroups found in anionic compounds. Of the cations (counter ions)associated with these polar groups, sodium, lithium and potassium impartwater solubility; ammonium and substituted ammonium ions provide bothwater and oil solubility; and, calcium, barium, and magnesium promoteoil solubility.

It is further discovered according to the invention that phosphateesters serve to enhance the surface activity and antimicrobial activityof a quaternary ammonium compound and are therefore suitable for use inthe activated compositions. In an aspect, a phosphosuccinateadducts/oligomer (PSO) are particularly well suited for the activatedcompositions according to the invention.

In an aspect, the anionic polymer or chelant is linear or branched. Inan aspect, the linear or branched anionic is a medium chain compoundhaving from 6-18 carbon chain length, preferably from 6-10 carbon chainlength, and more preferably from 6-9 carbon chain length. In an aspect,the linear or branched, medium chain anionic is alkoxylated orun-alkoxylated. In an aspect, the anionic polymer or chelant is acarboxylate. In a still further alternative aspect, the anionic polymeror chelant is a sulfonate and/or sulfate.

In an aspect, the anionic polymer or chelant suitable for use in thepresent compositions include carboxylates. Anionic carboxylate suitablefor use in the present compositions include carboxylic acids (andsalts), such as alkanoic acids (and alkanoates), ester carboxylic acids(e.g. alkyl succinates), ether carboxylic acids, sulfonated fatty acids,such as sulfonated oleic acid, and the like. Such carboxylates includealkyl ethoxy carboxylates, alkyl aryl ethoxy carboxylates, and alkylpolyethoxy polycarboxylates. Secondary carboxylates useful in thepresent compositions include those which contain a carboxyl unitconnected to a secondary carbon. The secondary carbon can be in a ringstructure, e.g. as in p-octyl benzoic acid, or as in alkyl-substitutedcyclohexyl carboxylates. The secondary carboxylate surfactants typicallycontain no ether linkages, no ester linkages and no hydroxyl groups.Further, they typically lack nitrogen atoms in the head-group(amphiphilic portion). Suitable secondary soap surfactants typicallycontain 11-13 total carbon atoms, although more carbons atoms (e.g., upto 16) can be present. Suitable carboxylates also include acylaminoacids (and salts), such as acylgluamates, acyl peptides, sarcosinates(e.g. N-acyl sarcosinates), taurates (e.g. N-acyl taurates and fattyacid amides of methyl tauride), and the like.

In an aspect, the anionic polymer or chelant suitable for use in thepresent compositions include polycarboxylates. Particularly suitablepolycarboxylates include, for example, polyacrylates and acrylamides.Further suitable polycarboxylates include, for example, polyacrylicacid, maleic/olefin copolymer, acrylic/maleic copolymer, polymethacrylicacid, acrylic acid-methacrylic acid copolymers, hydrolyzedpolyacrylamide, hydrolyzed polymethacrylamide, hydrolyzedpolyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile,hydrolyzed polymethacrylonitrile, hydrolyzedacrylonitrile-methacrylonitrile copolymers, polymaleic acid, polyfumaricacid, copolymers of acrylic and itaconic acid, phosphinopolycarboxylate, acid or salt forms thereof, mixtures thereof, and thelike. A suitable commercially available maleic homopolymer is AquatreatAR-801 (low molecular weight partially neutralized maleic homopolymer).In another aspect, hydrated or water soluble salts or partial salts ofthese polymers or copolymers such as their respective alkali metal (forexample, sodium or potassium) or ammonium salts may also be used. Theweight average molecular weight of the polymers is from about 4000 toabout 12,000. A suitable commercially available polyacrylic acidpolymers is Acusol 445N, available from Rohm & Haas LLC. Preferredpolymers include polyacrylic acid, the partial sodium salts ofpolyacrylic acid or sodium polyacrylate having an average molecularweight within the range of 4000 to 8000.

Suitable anionics include alkyl or alkylaryl ethoxy carboxylates of thefollowing formula: R—O—(CH₂CH₂O)_(n)(CH₂)_(m)—CO₂X in which R is aC8-C22 alkyl group or

in which R.sup.1 is a C4-C16 alkyl group; n is an integer of 1-20; m isan integer of 1-3; and X is a counter ion, such as hydrogen, sodium,potassium, lithium, ammonium, or an amine salt such as monoethanolamine,diethanolamine or triethanolamine. In some embodiments, n is an integerof 4 to 10 and m is 1. In some embodiments, R is a C8-C16 alkyl group.In some embodiments, R is a C12-C14 alkyl group, n is 4, and m is 1.

Such alkyl and alkylaryl ethoxy carboxylates are commercially available.These ethoxy carboxylates are typically available as the acid forms,which can be readily converted to the anionic or salt form.

In an aspect, the anionic polymer or chelant suitable for use in thepresent compositions include sulfonates and/or sulfates. In an aspect,the anionic suitable for use in the present compositions include alkylether sulfates, alkyl sulfates, the linear and branched primary andsecondary alkyl sulfates, alkyl ethoxysulfates, fatty oleyl glycerolsulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17acyl-N—(C1-C4 alkyl) and —N—(C1-C2 hydroxyalkyl) glucamine sulfates, andsulfates of alkylpolysaccharides such as the sulfates ofalkylpolyglucoside, and the like. Also included are the alkyl sulfates,alkyl poly(ethyleneoxy) ether sulfates and aromatic poly(ethyleneoxy)sulfates such as the sulfates or condensation products of ethylene oxideand nonyl phenol (usually having 1 to 6 oxyethylene groups permolecule). Anionic sulfonates suitable for use in the presentcompositions also include alkyl sulfonates, the linear and branchedprimary and secondary alkyl sulfonates, and the aromatic sulfonates withor without substituents.

In some embodiments, the compositions of the present invention includeone or more anionic chelating agents in combination with the quaternaryammonium compound to provide the surface active complex. Chelatingagents include, for example, chelating agents or sequestrants. Suitablesequestrants include, but are not limited to, organic chelatingcompounds that sequester metal ions in solution, particularly transitionmetal ions. Such sequestrants include organic amino- orhydroxy-polyphosphonic acid complexing agents (either in acid or solublesalt forms), carboxylic acids (e.g., polymeric polycarboxylate),hydroxycarboxylic acids, aminocarboxylic acids, or heterocycliccarboxylic acids, e.g., pyridine-2,6-dicarboxylic acid (dipicolinicacid).

Chelants can include sequestrants such as phosphonic acid or phosphonatesalt. Suitable phosphonic acids and phosphonate salts include HEDP;ethylenediamine tetrakis methylenephosphonic acid (EDTMP);diethylenetriamine pentakis methylenephosphonic acid (DTPMP);cyclohexane-1,2-tetramethylene phosphonic acid; amino[tri(methylenephosphonic acid)]; (ethylene diamine[tetra methylene-phosphonic acid)];2-phosphene butane-1,2,4-tricarboxylic acid; or salts thereof, such asthe alkali metal salts, ammonium salts, or alkyloyl amine salts, such asmono, di, or tetra-ethanolamine salts; picolinic, dipicolinic acid ormixtures thereof. In some embodiments, organic phosphonates, e.g, HEDPare included in the compositions of the present invention. Commerciallyavailable food additive chelating agents include phosphonates sold underthe trade name DEQUEST® including, for example,1-hydroxyethylidene-1,1-diphosphonic acid, available from MonsantoIndustrial Chemicals Co., St. Louis, Mo., as DEQUEST® 2010;amino(tri(methylenephosphonic acid)), (N[CH₂PO₃H₂]₃), available fromMonsanto as DEQUEST® 2000; ethylenediamine[tetra(methylenephosphonicacid)] available from Monsanto as DEQUEST® 2041; and2-phosphonobutane-1,2,4-tricarboxylic acid available from Mobay ChemicalCorporation, Inorganic Chemicals Division, Pittsburgh, Pa., as BayhibitAM.

Chelants can further aminocarboxylic acid type or aminocarboxylates orderivatives. Suitable aminocarboxylic acid type sequestrants include theacids or alkali metal salts thereof, e.g., amino acetates and saltsthereof. Suitable aminocarboxylates include N-hydroxyethylaminodiaceticacid; hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid(NTA); ethylenediaminetetraacetic acid (EDTA);N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA);diethylenetriaminepentaacetic acid (DTPA); and Alanine-N,N-diaceticacid; and the like; and mixtures thereof. Various biodegradableaminocarboxylate or derivative thereof are suitable for use as chelatingagents, including for example, methyl glycine diacetic acid (MGDA)available as Trilon M® from BASF.

An effective amount of the anionic polymer or chelant is provided incombination with the quaternary ammonium compound to provide synergisticantimicrobial and sanitizing efficacy. Suitable concentrations of theanionic polymer or chelant in a formulation composition include fromabout 0.01 to about 50 wt %, or from about 0.1 to about 50 wt-%. Withoutbeing limited according to the invention, all ranges recited areinclusive of the numbers defining the range and include each integerwithin the defined range. In certain embodiments of the invention, theanionic polymer or chelant may be an acidic compound and therefore maybe suitable for use as an acidulant and the polymer or chelant of thepresent invention, such as for example GLDA and HEDP.

Suitable concentrations of the anionic polymer or chelant in a usesolution include between about 1 ppm and about 500 ppm, 5 ppm and about250 ppm, 10 ppm and about 100 ppm, 20 ppm and about 100 ppm, 25 ppm andabout 100 ppm, 10 ppm and about 50 ppm, 20 ppm and about 50 ppm, 25 ppmand about 50 ppm, or about 50 ppm and about 100 ppm. Without beinglimited according to the invention, all ranges recited are inclusive ofthe numbers defining the range and include each integer within thedefined range.

According to embodiments of the invention, the anionic polymer orchelant may be provided in a concentrated composition in the amountbetween about 0.0001 wt.-%-50 wt.-%, from about 0.001 wt.-%-50 wt.-%,from about 0.01 wt.-%-50 wt.-%, from about 0.1 wt.-%-50 wt.-%, fromabout 0.1 wt.-%-30 wt.-%, from about 1 wt.-%-30 wt.-%, from about 0.1wt.-%-20 wt.-%, or from about 1 wt.-%-20 wt.-%. In addition, withoutbeing limited according to the invention, all ranges recited areinclusive of the numbers defining the range and include each integerwithin the defined range.

Additional Optional Components

The components of the compositions can further be combined with variousfunctional components. In some embodiments, the compositions includingthe quaternary ammonium compounds and anionic surfactants make up alarge amount, or even substantially all of the total weight of thecomposition. For example, in some embodiments few or no additionalfunctional ingredients are disposed therein. In other embodiments,additional functional ingredients may be included in the compositions.The functional ingredients provide desired properties andfunctionalities to the compositions. For the purpose of thisapplication, the term “functional ingredient” includes a material thatwhen dispersed or dissolved in the aqueous use solution provides abeneficial property in a particular use. Some particular examples offunctional materials are discussed in more detail below, although theparticular materials discussed are given by way of example only, andthat a broad variety of other functional ingredients may be used.

In some embodiments, the compositions may include additional functionalingredients including, for example, additional surfactants, thickenersand/or viscosity modifiers, solvents, solubility modifiers, humectants,metal protecting agents, stabilizing agents, e.g., chelating agents orsequestrants, corrosion inhibitors, sequestrants and/or chelatingagents, solidifying agent, sheeting agents, pH modifying components,including alkalinity and/or acidity sources, aesthetic enhancing agents(i.e., colorants, odorants, or perfumes), other cleaning agents,hydrotropes or couplers, buffers, and the like. Additionally, thecompositions can be used in conjunction with one or more conventionalcleaning agents, e.g., an alkaline detergent.

According to embodiments of the invention, the various additionalfunctional ingredients may be provided in a composition in the amountfrom about 0 wt.-%-90 wt.-%, from about 0 wt.-%-75 wt.-%, from about 0wt.-%-50 wt.-%, from about 0.01 wt.-%-50 wt.-%, from about 0.1 wt.-%-50wt.-%, from about 1 wt.-%-50 wt.-%, from about 1 wt.-%-30 wt.-%, fromabout 1 wt.-%-25 wt.-%, or from about 1 wt.-%-20 wt.-%. In addition,without being limited according to the invention, all ranges recited areinclusive of the numbers defining the range and include each integerwithin the defined range. In certain preferred embodiments, thecompositions of the invention do not include certain additionalfunctional ingredients. In an aspect the compositions do not includehalides. In an aspect the compositions do not include oxidants.

Alkalinity and/or Acidity Source

In some embodiments, the compositions of the present invention includean alkalinity source and/or acidulant. In a preferred embodiment, thecompositions of the present invention include an acidulant. Theacidulant can be effective to form a concentrate composition or a usesolution with a desired acidic to neutral pH. The acidulant can beeffective to form a use composition with pH of about 7, about 6 or less,about 5 or less, about 4, about 4 or less, about 3, about 3 or less,about 2, about 2 or less, or the like. In some embodiments, depending onthe anionic surfactant employed in the composition, an acidulant isincluded in the composition. In an embodiment, an acidulant is employedin combination with linear short chain carboxylates (e.g. pH 3-5) and/orfor branched/alkoxylated carboxylates having a broader pH.

In an embodiment, the acidulant includes an inorganic acid. Suitableinorganic acids include, but are not limited to, sulfuric acid, sodiumbisulfate, phosphoric acid, nitric acid, and hydrochloric acid. In someembodiments, the acidulant includes an organic acid. Suitable organicacids include, but are not limited to, methane sulfonic acid, ethanesulfonic acid, propane sulfonic acid, butane sulfonic acid, xylenesulfonic acid, benzene sulfonic acid, formic acid, acetic acid, mono,di, or tri-carboxylic acids (succinic, citric), picolinic acid,dipicolinic acid, and mixtures thereof. In some embodiments, thecompositions of the present invention are free or substantially free ofa phosphorous based acid. In some embodiments, acidulant selected canalso function as a stabilizing agent. Thus, the compositions of thepresent invention can be substantially free of an additional stabilizingagent.

In certain embodiments, the present composition includes about 0 toabout 80 wt-% acidulant, about 0.5 wt-% to about 80 wt-% acidulant,about 0.1 to about 50 wt %, about 1 to about 50 wt %, or about 5 toabout 30 wt-% acidulant. It is to be understood that all values andranges between these values and ranges are encompassed by thecompositions of the present invention.

Stabilizing Agents

In some embodiments, the compositions of the present invention includeone or more stabilizing agents. In some embodiments, an acidicstabilizing agent can be used. Thus, in some embodiments, thecompositions of the present invention can be substantially free of anadditional acidulant. Suitable stabilizing agents include, for example,chelating agents or sequestrants. Suitable sequestrants include, but arenot limited to, organic chelating compounds that sequester metal ions insolution, particularly transition metal ions. Such sequestrants includeorganic amino- or hydroxy-polyphosphonic acid complexing agents (eitherin acid or soluble salt forms), carboxylic acids (e.g., polymericpolycarboxylate), hydroxycarboxylic acids, aminocarboxylic acids, orheterocyclic carboxylic acids, e.g., pyridine-2,6-dicarboxylic acid(dipicolinic acid).

In some embodiments, the compositions of the present invention includedipicolinic acid as a stabilizing agent. Compositions includingdipicolinic acid can be formulated to be free or substantially free ofphosphorous. It has also been observed that the inclusion of dipicolinicacid in a composition of the present invention aids in achieving thephase stability of the compositions, compared to other conventionalstabilizing agents, e.g., 1-hydroxy ethylidene-1,1-diphosphonic acid(CH₃C(PO₃H₂)₂OH) (HEDP).

In other embodiments, the sequestrant can be or include phosphonic acidor phosphonate salt. Suitable phosphonic acids and phosphonate saltsinclude HEDP; ethylenediamine tetrakis methylenephosphonic acid (EDTMP);diethylenetriamine pentakis methylenephosphonic acid (DTPMP);cyclohexane-1,2-tetramethylene phosphonic acid; amino[tri(methylenephosphonic acid)]; (ethylene diamine[tetra methylene-phosphonic acid)];2-phosphene butane-1,2,4-tricarboxylic acid; or salts thereof, such asthe alkali metal salts, ammonium salts, or alkyloyl amine salts, such asmono, di, or tetra-ethanolamine salts; picolinic, dipicolinic acid ormixtures thereof. In some embodiments, organic phosphonates, e.g, HEDPare included in the compositions of the present invention. Commerciallyavailable food additive chelating agents include phosphonates sold underthe trade name DEQUEST® including, for example,1-hydroxyethylidene-1,1-diphosphonic acid, available from MonsantoIndustrial Chemicals Co., St. Louis, Mo., as DEQUEST® 2010;amino(tri(methylenephosphonic acid)), (N[CH₂PO₃H₂]₃), available fromMonsanto as DEQUEST® 2000; ethylenediamine[tetra(methylenephosphonicacid)] available from Monsanto as DEQUEST® 2041; and2-phosphonobutane-1,2,4-tricarboxylic acid available from Mobay ChemicalCorporation, Inorganic Chemicals Division, Pittsburgh, Pa., as BayhibitAM.

The sequestrant can be or include aminocarboxylic acid type sequestrant.Suitable aminocarboxylic acid type sequestrants include the acids oralkali metal salts thereof, e.g., amino acetates and salts thereof.Suitable aminocarboxylates include N-hydroxyethylaminodiacetic acid;hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA);ethylenediaminetetraacetic acid (EDTA);N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA);diethylenetriaminepentaacetic acid (DTPA); and Alanine-N,N-diaceticacid; and the like; and mixtures thereof.

The sequestrant can be or include a polycarboxylate. Suitablepolycarboxylates include, for example, polyacrylic acid, maleic/olefincopolymer, acrylic/maleic copolymer, polymethacrylic acid, acrylicacid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzedpolymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers,hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile,hydrolyzed acrylonitrile-methacrylonitrile copolymers, polymaleic acid,polyfumaric acid, copolymers of acrylic and itaconic acid, phosphinopolycarboxylate, acid or salt forms thereof, mixtures thereof, and thelike.

In certain embodiments, the present composition includes about 0 toabout 10 wt-% stabilizing agent, about 0.01 to about 10 wt-% stabilizingagent, about 0.4 to about 4 wt-% stabilizing agent, about 0.6 to about 3wt-% stabilizing agent, about 1 to about 2 wt-% stabilizing agent. It isto be understood that all values and ranges within these values andranges are encompassed by the present invention.

Wetting or Defoaming Agents

Also useful in the compositions of the invention are wetting anddefoaming agents. Wetting agents function to increase the surfacecontact or penetration activity of the antimicrobial composition of theinvention. Wetting agents which can be used in the composition of theinvention include any of those constituents known within the art toraise the surface activity of the composition of the invention. Inaspects of the invention various quaternary ammonium compounds aresuitable for the rinse aid and sanitizing rinse aid application withoutthe use of further defoamers in the formulation. In other embodimentsemploying commercially-available quaternary ammonium compounds, adefoamer is preferred in the composition or in combination with thecomposition, such as for example compositions employing Bardac 2250,Bardac MB50, and Bardac 205M.

Generally, defoamers which can be used in accordance with the inventionpreferably include alcohol alkoxylates and EO/PO block copolymers. Insome embodiments, the compositions of the present invention can includeantifoaming agents or defoamers which are of food grade quality giventhe application of the method of the invention. To this end, one of themore effective antifoaming agents includes silicones. Silicones such asdimethyl silicone, glycol polysiloxane, methylphenol polysiloxane,trialkyl or tetralkyl silanes, hydrophobic silica defoamers and mixturesthereof can all be used in defoaming applications. Commercial defoamerscommonly available include silicones such as Ardefoam® from ArmourIndustrial Chemical Company which is a silicone bound in an organicemulsion; Foam Kill® or Kresseo® available from Krusable ChemicalCompany which are silicone and non-silicone type defoamers as well assilicone esters; and Anti-Foam A® and DC-200 from Dow CorningCorporation which are both food grade type silicones among others. Thesedefoamers can be present at a concentration range from about 0.01 wt-%to 20 wt-%, 0.01 wt-% to 20 wt-%, from about 0.01 wt-% to 5 wt-%, orfrom about 0.01 wt-% to about 1 wt-%.

Thickening or Gelling Agents

The compositions of the present invention can include any of a varietyof known thickeners. Suitable thickeners include natural gums such asxanthan gum, guar gum, or other gums from plant mucilage; polysaccharidebased thickeners, such as alginates, starches, and cellulosic polymers(e.g., carboxymethyl cellulose); polyacrylates thickeners; andhydrocolloid thickeners, such as pectin. In an embodiment, the thickenerdoes not leave contaminating residue on the surface of an object. Forexample, the thickeners or gelling agents can be compatible with food orother sensitive products in contact areas. Generally, the concentrationof thickener employed in the present compositions or methods will bedictated by the desired viscosity within the final composition. However,as a general guideline, the viscosity enhancer or thickener within thepresent composition ranges from about 0.1 wt-% to about 5 wt-%, fromabout 0.1 wt-% to about 1.0 wt-%, or from about 0.1 wt-% to about 0.5wt-%.

Additional Surfactants

The antimicrobial compositions and/or inactivated antimicrobialcompositions according to the invention may include additionalsurfactants. In a particular aspect, nonionic surfactants areparticularly useful for applications of use requiring additionaldefoaming. In some aspects, a nonionic surfactant may be desired incombination with the compositions of the invention (such as included ina detergent formulation employed in combination therewith). For example,in certain embodiments, such as food soil defoaming applications, anonionic surfactant may be desirable to preferably include alcoholalkoxylates and EO/PO block copolymers.

Useful nonionic surfactants are generally characterized by the presenceof an organic hydrophobic group and an organic hydrophilic group and aretypically produced by the condensation of an organic aliphatic, alkylaromatic or polyoxyalkylene hydrophobic compound with a hydrophilicalkaline oxide moiety which in common practice is ethylene oxide or apolyhydration product thereof, polyethylene glycol. Practically anyhydrophobic compound having a hydroxyl, carboxyl, amino, or amido groupwith a reactive hydrogen atom can be condensed with ethylene oxide, orits polyhydration adducts, or its mixtures with alkoxylenes such aspropylene oxide to form a nonionic surface-active agent. The length ofthe hydrophilic polyoxyalkylene moiety which is condensed with anyparticular hydrophobic compound can be readily adjusted to yield a waterdispersible or water soluble compound having the desired degree ofbalance between hydrophilic and hydrophobic properties. Useful nonionicsurfactants include:

Block polyoxypropylene-polyoxyethylene polymeric compounds based uponpropylene glycol, ethylene glycol, glycerol, trimethylolpropane, andethylenediamine as the initiator reactive hydrogen compound. Examples ofpolymeric compounds made from a sequential propoxylation andethoxylation of initiator are commercially available under the tradenames Pluronic® and Tetronic® manufactured by BASF Corp. Pluronic®compounds are difunctional (two reactive hydrogens) compounds formed bycondensing ethylene oxide with a hydrophobic base formed by the additionof propylene oxide to the two hydroxyl groups of propylene glycol. Thishydrophobic portion of the molecule weighs from about 1,000 to about4,000. Ethylene oxide is then added to sandwich this hydrophobe betweenhydrophilic groups, controlled by length to constitute from about 10% byweight to about 80% by weight of the final molecule. Tetronic® compoundsare tetra-flinctional block copolymers derived from the sequentialaddition of propylene oxide and ethylene oxide to ethylenediamine. Themolecular weight of the propylene oxide hydrotype ranges from about 500to about 7,000; and, the hydrophile, ethylene oxide, is added toconstitute from about 10% by weight to about 80% by weight of themolecule.

Condensation products of one mole of alkyl phenol wherein the alkylchain, of straight chain or branched chain configuration, or of singleor dual alkyl constituent, contains from about 8 to about 18 carbonatoms with from about 3 to about 50 moles of ethylene oxide. The alkylgroup can, for example, be represented by diisobutylene, di-amyl,polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactantscan be polyethylene, polypropylene, and polybutylene oxide condensatesof alkyl phenols. Examples of commercial compounds of this chemistry areavailable on the market under the trade names Igepal® manufactured byRhodiaand Triton® manufactured by Dow Chemical Company.

Condensation products of one mole of a saturated or unsaturated,straight or branched chain alcohol having from about 6 to about 24carbon atoms with from about 3 to about 50 moles of ethylene oxide. Thealcohol moiety can consist of mixtures of alcohols in the abovedelineated carbon range or it can consist of an alcohol having aspecific number of carbon atoms within this range. Examples of likecommercial surfactant are available under the trade names Neodol®manufactured by Shell Chemical Co. and Alfonic® manufactured by SasolNorth America Inc.

Condensation products of one mole of saturated or unsaturated, straightor branched chain carboxylic acid having from about 8 to about 18 carbonatoms with from about 6 to about 50 moles of ethylene oxide. The acidmoiety can consist of mixtures of acids in the above defined carbonatoms range or it can consist of an acid having a specific number ofcarbon atoms within the range.

In addition to ethoxylated carboxylic acids, commonly calledpolyethylene glycol esters, other alkanoic acid esters formed byreaction with glycerides, glycerin, and polyhydric (saccharide orsorbitan/sorbitol) alcohols have application in this invention forspecialized embodiments, particularly indirect food additiveapplications. All of these ester moieties have one or more reactivehydrogen sites on their molecule which can undergo further acylation orethylene oxide (alkoxide) addition to control the hydrophilicity ofthese substances. Care must be exercised when adding these fatty estersor acylated carbohydrates to compositions of the present inventioncontaining amylase and/or lipase enzymes because of potentialincompatibility.

Examples of nonionic low foaming surfactants include:

Compounds from (1) which are modified, essentially reversed, by addingethylene oxide to ethylene glycol to provide a hydrophile of designatedmolecular weight; and, then adding propylene oxide to obtain hydrophobicblocks on the outside (ends) of the molecule. The hydrophobic portion ofthe molecule weighs from about 1,000 to about 3,100 with the centralhydrophile including 10% by weight to about 80% by weight of the finalmolecule. These reverse Pluronics® are manufactured by BASF Corporationunder the trade name Pluronic® R surfactants. Likewise, the Tetronic® Rsurfactants are produced by BASF Corporation by the sequential additionof ethylene oxide and propylene oxide to ethylenediamine. Thehydrophobic portion of the molecule weighs from about 2,100 to about6,700 with the central hydrophile including 10% by weight to 80% byweight of the final molecule.

Compounds from groups (1), (2), (3) and (4) which are modified by“capping” or “end blocking” the terminal hydroxy group or groups (ofmulti-functional moieties) to reduce foaming by reaction with a smallhydrophobic molecule such as propylene oxide, butylene oxide, benzylchloride; and, short chain fatty acids, alcohols or alkyl halidescontaining from 1 to about 5 carbon atoms; and mixtures thereof. Alsoincluded are reactants such as thionyl chloride which convert terminalhydroxy groups to a chloride group. Such modifications to the terminalhydroxy group may lead to all-block, block-heteric, heteric-block orall-heteric nonionics.

Additional examples of effective low foaming nonionics include:

The alkylphenoxypolyethoxyalkanols of U.S. Pat. No. 2,903,486 issuedSep. 8, 1959 to Brown et al. and represented by the formula

in which R is an alkyl group of 8 to 9 carbon atoms, A is an alkylenechain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is aninteger of 1 to 10.

The polyalkylene glycol condensates of U.S. Pat. No. 3,048,548 issuedAug. 7, 1962 to Martin et al. having alternating hydrophilic oxyethylenechains and hydrophobic oxypropylene chains where the weight of theterminal hydrophobic chains, the weight of the middle hydrophobic unitand the weight of the linking hydrophilic units each represent aboutone-third of the condensate.

The defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178issued May 7, 1968 to Lissant et al. having the general formulaZ[(OR)_(n)OH]_(z) wherein Z is alkoxylatable material, R is a radicalderived from an alkaline oxide which can be ethylene and propylene and nis an integer from, for example, 10 to 2,000 or more and z is an integerdetermined by the number of reactive oxyalkylatable groups.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,677,700, issued May 4, 1954 to Jackson et al. corresponding to theformula Y(C₃H₆O)_(n)(C₂H₄O)_(m)H wherein Y is the residue of organiccompound having from about 1 to 6 carbon atoms and one reactive hydrogenatom, n has an average value of at least about 6.4, as determined byhydroxyl number and m has a value such that the oxyethylene portionconstitutes about 10% to about 90% by weight of the molecule.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,674,619, issued Apr. 6, 1954 to Lundsted et al. having the formulaY[(C₃H₆O_(n)(C₂H₄O)_(m)H]_(x) wherein Y is the residue of an organiccompound having from about 2 to 6 carbon atoms and containing x reactivehydrogen atoms in which x has a value of at least about 2, n has a valuesuch that the molecular weight of the polyoxypropylene hydrophobic baseis at least about 900 and m has value such that the oxyethylene contentof the molecule is from about 10% to about 90% by weight. Compoundsfalling within the scope of the definition for Y include, for example,propylene glycol, glycerine, pentaerythritol, trimethylolpropane,ethylenediamine and the like. The oxypropylene chains optionally, butadvantageously, contain small amounts of ethylene oxide and theoxyethylene chains also optionally, but advantageously, contain smallamounts of propylene oxide.

Additional conjugated polyoxyalkylene surface-active agents which areadvantageously used in the compositions of this invention correspond tothe formula: P[(C₃H₆O)_(n)(C₂H₄O)_(m)H]_(x) wherein P is the residue ofan organic compound having from about 8 to 18 carbon atoms andcontaining x reactive hydrogen atoms in which x has a value of 1 or 2, nhas a value such that the molecular weight of the polyoxyethyleneportion is at least about 44 and m has a value such that theoxypropylene content of the molecule is from about 10% to about 90% byweight. In either case the oxypropylene chains may contain optionally,but advantageously, small amounts of ethylene oxide and the oxyethylenechains may contain also optionally, but advantageously, small amounts ofpropylene oxide.

Polyhydroxy fatty acid amide surfactants suitable for use in the presentcompositions include those having the structural formula R₂CON_(R1)Z inwhich: R1 is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl,ethoxy, propoxy group, or a mixture thereof; R₂ is a C₅-C₃₁ hydrocarbyl,which can be straight-chain; and Z is a polyhydroxyhydrocarbyl having alinear hydrocarbyl chain with at least 3 hydroxyls directly connected tothe chain, or an alkoxylated derivative (preferably ethoxylated orpropoxylated) thereof. Z can be derived from a reducing sugar in areductive amination reaction; such as a glycityl moiety.

The alkyl ethoxylate condensation products of aliphatic alcohols withfrom about 0 to about 25 moles of ethylene oxide are suitable for use inthe present compositions. The alkyl chain of the aliphatic alcohol caneither be straight or branched, primary or secondary, and generallycontains from 6 to 22 carbon atoms.

The ethoxylated C₆-C₁₈ fatty alcohols and C₆-C₁₈ mixed ethoxylated andpropoxylated fatty alcohols are suitable surfactants for use in thepresent compositions, particularly those that are water soluble.Suitable ethoxylated fatty alcohols include the C₆-C₁₈ ethoxylated fattyalcohols with a degree of ethoxylation of from 3 to 50.

Suitable nonionic alkyl polysaccharide surfactants, particularly for usein the present compositions include those disclosed in U.S. Pat. No.4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include ahydrophobic group containing from about 6 to about 30 carbon atoms and apolysaccharide, e.g., a polyglycoside, hydrophilic group containing fromabout 1.3 to about 10 saccharide units. Any reducing saccharidecontaining 5 or 6 carbon atoms can be used, e.g., glucose, galactose andgalactosyl moieties can be substituted for the glucosyl moieties.(Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc.positions thus giving a glucose or galactose as opposed to a glucosideor galactoside.) The intersaccharide bonds can be, e.g., between the oneposition of the additional saccharide units and the 2-, 3-, 4-, and/or6-positions on the preceding saccharide units.

Fatty acid amide surfactants suitable for use the present compositionsinclude those having the formula: R₆CON(R₇)₂ in which R₆ is an alkylgroup containing from 7 to 21 carbon atoms and each R₇ is independentlyhydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, or —(C₂H₄O)_(x)H, where x isin the range of from 1 to 3.

A useful class of non-ionic surfactants include the class defined asalkoxylated amines or, most particularly, alcoholalkoxylated/aminated/alkoxylated surfactants. These non-ionicsurfactants may be at least in part represented by the general formulae:R²⁰—(PO)_(S)N-(EO)_(t)H, R²⁰—(PO)_(S)N-(EO)_(t)H(EO)_(t)H, andR²⁰—N(EO)_(t)H; in which R²⁰ is an alkyl, alkenyl or other aliphaticgroup, or an alkyl-aryl group of from 8 to 20, preferably 12 to 14carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20,preferably 2-5, t is 1-10, preferably 2-5, and u is 1-10, preferably2-5. Other variations on the scope of these compounds may be representedby the alternative formula: R²⁰--(PO)_(V)—N[(EO)_(w)H][(EO)_(w)H] inwhich R²⁰ is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4(preferably 2)), and w and z are independently 1-10, preferably 2-5.These compounds are represented commercially by a line of products soldby Huntsman Chemicals as nonionic surfactants. A preferred chemical ofthis class includes Surfonic® PEA 25 Amine Alkoxylate. Preferrednonionic surfactants for the compositions of the invention includealcohol alkoxylates, EO/PO block copolymers, alkylphenol alkoxylates,and the like.

The treatise Nonionic Surfactants, edited by Schick, M. J., Vol. 1 ofthe Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is anexcellent reference on the wide variety of nonionic compounds generallyemployed in the practice of the present invention. A typical listing ofnonionic classes, and species of these surfactants, is given in U.S.Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975.Further examples are given in “Surface Active Agents and detergents”(Vol. I and II by Schwartz, Perry and Berch).

Semi-Polar Nonionic Surfactants

The semi-polar type of nonionic surface active agents are another classof nonionic surfactant useful in compositions of the present invention.Generally, semi-polar nonionics are high foamers and foam stabilizers,which can limit their application in CIP systems. However, withincompositional embodiments of this invention designed for high foamcleaning methodology, semi-polar nonionics would have immediate utility.The semi-polar nonionic surfactants include the amine oxides, phosphineoxides, sulfoxides and their alkoxylated derivatives.

Amine oxides are tertiary amine oxides corresponding to the generalformula:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹, R², and R³ may be aliphatic, aromatic, heterocyclic, alicyclic,or combinations thereof. Generally, for amine oxides of detergentinterest, R¹ is an alkyl radical of from about 8 to about 24 carbonatoms; R² and R³ are alkyl or hydroxyalkyl of 1-3 carbon atoms or amixture thereof; R² and R³ can be attached to each other, e.g. throughan oxygen or nitrogen atom, to form a ring structure; R⁴ is an alkalineor a hydroxyalkylene group containing 2 to 3 carbon atoms; and n rangesfrom 0 to about 20.

Useful water soluble amine oxide surfactants are selected from thecoconut or tallow alkyl di-(lower alkyl) amine oxides, specific examplesof which are dodecyldimethylamine oxide, tridecyldimethylamine oxide,etradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Useful semi-polar nonionic surfactants also include the water solublephosphine oxides having the following structure:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹ is an alkyl, alkenyl or hydroxyalkyl moiety ranging from 10 toabout 24 carbon atoms in chain length; and, R² and R³ are each alkylmoieties separately selected from alkyl or hydroxyalkyl groupscontaining 1 to 3 carbon atoms.

Examples of useful phosphine oxides include dimethyldecylphosphineoxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphoneoxide, dimethylhexadecylphosphine oxide,diethyl-2-hydroxyoctyldecylphosphine oxide,bis(2-hydroxyethyl)dodecylphosphine oxide, andbis(hydroxymethyl)tetradecylphosphine oxide.

Semi-polar nonionic surfactants useful herein also include the watersoluble sulfoxide compounds which have the structure:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹ is an alkyl or hydroxyalkyl moiety of about 8 to about 28 carbonatoms, from 0 to about 5 ether linkages and from 0 to about 2 hydroxylsubstituents; and R² is an alkyl moiety consisting of alkyl andhydroxyalkyl groups having 1 to 3 carbon atoms.

Useful examples of these sulfoxides include dodecyl methyl sulfoxide;3-hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methylsulfoxide; and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

Semi-polar nonionic surfactants for the compositions of the inventioninclude dimethyl amine oxides, such as lauryl dimethyl amine oxide,myristyl dimethyl amine oxide, cetyl dimethyl amine oxide, combinationsthereof, and the like. Useful water soluble amine oxide surfactants areselected from the octyl, decyl, dodecyl, isododecyl, coconut, or tallowalkyl di-(lower alkyl) amine oxides, specific examples of which areoctyldimethylamine oxide, nonyldimethylamine oxide, decyldimethylamineoxide, undecyldimethylamine oxide, dodecyldimethylamine oxide,iso-dodecyldimethyl amine oxide, tridecyldimethylamine oxide,tetradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Suitable nonionic surfactants suitable for use with the compositions ofthe present invention include alkoxylated surfactants. Suitablealkoxylated surfactants include EO/PO copolymers, capped EO/POcopolymers, alcohol alkoxylates, capped alcohol alkoxylates, mixturesthereof, or the like. Suitable alkoxylated surfactants for use assolvents include EO/PO block copolymers, such as the Pluronic® andreverse Pluronic® surfactants; alcohol alkoxylates, such as Dehypon®LS-54 (R-(EO)₅(PO)₄) and Dehypon® LS-36 (R-(EO)₃(PO)₆); and cappedalcohol alkoxylates, such as Plurafac® LF221 and Tegoten® EC11; mixturesthereof, or the like.

Sequestrants

The composition can contain an organic or inorganic sequestrant ormixtures of sequestrants. Organic sequestrants such as sodium citrate,the alkali metal salts of nitrilotriacetic acid (NTA), dicarboxymethylglutamic acid tetrasodium salt (GLDA), EDTA, alkali metal gluconates,polyelectrolytes such as a polyacrylic acid, and the like can be usedherein. The most preferred sequestrants are organic sequestrants such assodium gluconate due to the compatibility of the sequestrant with theformulation base.

The present invention can also incorporate sequestrants to includematerials such as, complex phosphate sequestrants, including sodiumtripolyphosphate, sodium hexametaphosphate, and the like, as well asmixtures thereof. Phosphates, the sodium condensed phosphate hardnesssequestering agent component functions as a water softener, a cleaner,and a detergent builder. Alkali metal (M) linear and cyclic condensedphosphates commonly have a M₂ O:P₂ O₅ mole ratio of about 1:1 to 2:1 andgreater. Typical polyphosphates of this kind are the preferred sodiumtripolyphosphate, sodium hexametaphosphate, sodium metaphosphate as wellas corresponding potassium salts of these phosphates and mixturesthereof. The particle size of the phosphate is not critical, and anyfinely divided or granular commercially available product can beemployed.

Solidification Agents or Hardening Agents

If it is desirous to prepare compositions of the invention as a solid, asolidification agent may be included into the composition. In someembodiments, the solidification agent can form and/or maintain thecomposition as a solid rinse aid composition. In other embodiments, thesolidification agent can solidify the composition without unacceptablydetracting from the eventual release of the active ingredients. Thesolidification agent can include, for example, an organic or inorganicsolid compound having a neutral inert character or making a functional,stabilizing or detersive contribution to the present composition.Suitable solidification agents include solid polyethylene glycol (PEG),solid polypropylene glycol, solid EO/PO block copolymer, amide, urea(also known as carbamide), nonionic surfactant (which can be employedwith a coupler), anionic surfactant, starch that has been madewater-soluble (e.g., through an acid or alkaline treatment process),cellulose that has been made water-soluble, inorganic agent, poly(maleicanhydride/methyl vinyl ether), polymethacrylic acid, other generallyfunctional or inert materials with high melting points, mixturesthereof, and the like.

Suitable glycol solidification agents include a solid polyethyleneglycol or a solid polypropylene glycol, which can, for example, havemolecular weight of about 1,400 to about 30,000. In certain embodiments,the solidification agent includes or is solid PEG, for example PEG 1500up to PEG 20,000. In certain embodiments, the PEG includes PEG 1450, PEG3350, PEG 4500, PEG 8000, PEG 20,000, and the like. Suitable solidpolyethylene glycols are commercially available from Union Carbide underthe tradename CARBOWAX.

Suitable amide solidification agents include stearic monoethanolamide,lauric diethanolamide, stearic diethanolamide, stearic monoethanolamide, cocodiethylene amide, an alkylamide, mixtures thereof, and thelike. In an embodiment, the present composition can include glycol(e.g., PEG) and amide.

Suitable inorganic solidification agents include phosphate salt (e.g.,alkali metal phosphate), sulfate salt (e.g., magnesium sulfate, sodiumsulfate or sodium bisulfate), acetate salt (e.g., anhydrous sodiumacetate), Borates (e.g., sodium borate), Silicates (e.g., theprecipitated or fumed forms (e.g., Sipernat 50® available from Degussa),carbonate salt (e.g., calcium carbonate or carbonate hydrate), otherknown hydratable compounds, mixtures thereof, and the like. In anembodiment, the inorganic solidification agent can include organicphosphonate compound and carbonate salt, such as an E-Form composition.

In some embodiments, the compositions of the present invention caninclude any agent or combination of agents that provide a requisitedegree of solidification and aqueous solubility can be included in thepresent compositions. In other embodiments, increasing the concentrationof the solidification agent in the present composition can tend toincrease the hardness of the composition. In yet other embodiments,decreasing the concentration of solidification agent can tend to loosenor soften the concentrate composition.

In some embodiments, the solidification agent can include any organic orinorganic compound that imparts a solid character to and/or controls thesoluble character of the present composition, for example, when placedin an aqueous environment. For example, a solidifying agent can providecontrolled dispensing if it has greater aqueous solubility compared toother ingredients in the composition. Urea can be one suchsolidification agent. By way of further example, for systems that canbenefit from less aqueous solubility or a slower rate of dissolution, anorganic nonionic or amide hardening agent may be appropriate.

In some embodiments, the compositions of the present invention caninclude a solidification agent that provides for convenient processingor manufacture of the present composition. For example, thesolidification agent can be selected to form a composition that canharden to a solid form under ambient temperatures of about 30 to about50° C. after mixing ceases and the mixture is dispensed from the mixingsystem, within about 1 minute to about 3 hours, or about 2 minutes toabout 2 hours, or about 5 minutes to about 1 hour.

In an exemplary aspect, a solid rinse aid may include an effectiveamount of a solidification agent or a hardening agent, as for example,urea which vary the solubility of the composition in an aqueous mediumduring use such that the rinse aid and/or other active ingredients maybe dispensed from the solid composition over an extended period of time.The composition may include a hardening agent in an amount in the rangeof up to about 50 wt %. In other embodiments, the hardening agent may bepresent in amount from about 20 wt % to about 40 wt %, or in the rangeof about 5 to about 15 wt %.

The compositions of the present invention can include solidificationagent at any effective amount. The amount of solidification agentincluded in the present composition can vary according to the type ofcomposition, the ingredients of the composition, the intended use of thecomposition, the quantity of dispensing solution applied to the solidcomposition over time during use, the temperature of the dispensingsolution, the hardness of the dispensing solution, the physical size ofthe solid composition, the concentration of the other ingredients, theconcentration of the cleaning agent in the composition, and other likefactors. Suitable amounts can include about 1 to about 99 wt-%, about1.5 to about 85 wt-%, about 2 to about 80 wt-%, about 10 to about 45wt-%, about 15% to about 40 wt-%, about 20% to about 30 wt-%, about 30%to about 70%, about 40% to about 60%, up to about 50 wt-%, about 40% toabout 50%.

Additional Exemplary Embodiments

In some aspects, the antimicrobial compositions or inactivatedantimicrobial compositions according to the invention may comprise,consist of and/or consist essentially of a quaternary ammonium compoundin an amount from about 0.001 wt-% to about 75 wt-%, and an anionicsurfactant or anionic polymer/chelant in an amount from about 0.0001wt-% to about 50 wt-%.

In some aspects, the antimicrobial compositions or inactivatedantimicrobial compositions according to the invention may comprise,consist of and/or consist essentially of a quaternary ammonium compoundin an amount from about 0.001 wt-% to about 75 wt-%, an anionicsurfactant or anionic polymer/chelant in an amount from about 0.0001wt-% to about 50 wt-%, and at least one additional functional ingredientselected from the group consisting of: an acidulant in an amount fromabout 0.1 wt-% to about 50 wt-%, a stabilizing agent in an amount fromabout 0.01 wt-% to about 10 wt-%, a defoamer in an amount from about0.01 wt-% to about 20 wt-%, a viscosity enhancer or thickener in anamount from about 0.1 wt-% to about 5 wt-%, an additional surfactant inan amount from about 0.01 wt-% to about 50 wt-%, a sequestrant in anamount from about 0.01 wt-% to about 50 wt-%, and a solidification agentin an amount from about 0.01 wt-% to about 50 wt-%.

In some aspects, the antimicrobial compositions or inactivatedantimicrobial compositions according to the invention may comprise,consist of and/or consist essentially of a quaternary ammonium compoundin an amount from about 0.001 wt-% to about 75 wt-%, an anionicsurfactant or anionic polymer/chelant in an amount from about 0.0001wt-% to about 50 wt-%, and at least two additional functionalingredients selected from the group consisting of: an acidulant in anamount from about 0.1 wt-% to about 50 wt-%, a stabilizing agent in anamount from about 0.01 wt-% to about 10 wt-%, a defoamer in an amountfrom about 0.01 wt-% to about 20 wt-%, a viscosity enhancer or thickenerin an amount from about 0.1 wt-% to about 5 wt-%, an additionalsurfactant in an amount from about 0.01 wt-% to about 50 wt-%, asequestrant in an amount from about 0.01 wt-% to about 50 wt-%, and asolidification agent in an amount from about 0.01 wt-% to about 50 wt-%.

In some aspects, the antimicrobial compositions or inactivatedantimicrobial compositions according to the invention may comprise,consist of and/or consist essentially of a quaternary ammonium compoundin an amount from about 0.001 wt-% to about 75 wt-%, an anionicsurfactant or anionic polymer/chelant in an amount from about 0.0001wt-% to about 50 wt-%, and at least three additional functionalingredients selected from the group consisting of: an acidulant in anamount from about 0.1 wt-% to about 50 wt-%, a stabilizing agent in anamount from about 0.01 wt-% to about 10 wt-%, a defoamer in an amountfrom about 0.01 wt-% to about 20 wt-%, a viscosity enhancer or thickenerin an amount from about 0.1 wt-% to about 5 wt-%, an additionalsurfactant in an amount from about 0.01 wt-% to about 50 wt-%, asequestrant in an amount from about 0.01 wt-% to about 50 wt-%, and asolidification agent in an amount from about 0.01 wt-% to about 50 wt-%.

In some aspects, the antimicrobial compositions or inactivatedantimicrobial compositions according to the invention may comprise,consist of and/or consist essentially of a quaternary ammonium compoundin an amount from about 0.001 wt-% to about 75 wt-%, an anionicsurfactant or anionic polymer/chelant in an amount from about 0.0001wt-% to about 50 wt-%, and at least four additional functionalingredients selected from the group consisting of: an acidulant in anamount from about 0.1 wt-% to about 50 wt-%, a stabilizing agent in anamount from about 0.01 wt-% to about 10 wt-%, a defoamer in an amountfrom about 0.01 wt-% to about 20 wt-%, a viscosity enhancer or thickenerin an amount from about 0.1 wt-% to about 5 wt-%, an additionalsurfactant in an amount from about 0.01 wt-% to about 50 wt-%, asequestrant in an amount from about 0.01 wt-% to about 50 wt-%, and asolidification agent in an amount from about 0.01 wt-% to about 50 wt-%.

In some aspects, the antimicrobial compositions or inactivatedantimicrobial compositions according to the invention may comprise,consist of and/or consist essentially of a quaternary ammonium compoundin an amount from about 0.001 wt-% to about 75 wt-%, an anionicsurfactant or anionic polymer/chelant in an amount from about 0.0001wt-% to about 50 wt-%, and at least five additional functionalingredients selected from the group consisting of: an acidulant in anamount from about 0.1 wt-% to about 50 wt-%, a stabilizing agent in anamount from about 0.01 wt-% to about 10 wt-%, a defoamer in an amountfrom about 0.01 wt-% to about 20 wt-%, a viscosity enhancer or thickenerin an amount from about 0.1 wt-% to about 5 wt-%, an additionalsurfactant in an amount from about 0.01 wt-% to about 50 wt-%, asequestrant in an amount from about 0.01 wt-% to about 50 wt-%, and asolidification agent in an amount from about 0.01 wt-% to about 50 wt-%.

In some aspects, the antimicrobial compositions or inactivatedantimicrobial compositions according to the invention may comprise,consist of and/or consist essentially of a quaternary ammonium compoundin an amount from about 0.001 wt-% to about 75 wt-%, an anionicsurfactant or anionic polymer/chelant in an amount from about 0.0001wt-% to about 50 wt-%, and at least six additional functionalingredients selected from the group consisting of: an acidulant in anamount from about 0.1 wt-% to about 50 wt-%, a stabilizing agent in anamount from about 0.01 wt-% to about 10 wt-%, a defoamer in an amountfrom about 0.01 wt-% to about 20 wt-%, a viscosity enhancer or thickenerin an amount from about 0.1 wt-% to about 5 wt-%, an additionalsurfactant in an amount from about 0.01 wt-% to about 50 wt-%, asequestrant in an amount from about 0.01 wt-% to about 50 wt-%, and asolidification agent in an amount from about 0.01 wt-% to about 50 wt-%.

In some aspects, the antimicrobial compositions or inactivatedantimicrobial compositions according to the invention may comprise,consist of and/or consist essentially of a quaternary ammonium compoundin an amount from about 0.001 wt-% to about 75 wt-%, an anionicsurfactant or anionic polymer/chelant in an amount from about 0.0001wt-% to about 50 wt-%, an acidulant in an amount from about 0.1 wt-% toabout 50 wt-%, a stabilizing agent in an amount from about 0.01 wt-% toabout 10 wt-%, a defoamer in an amount from about 0.01 wt-% to about 20wt-%, a viscosity enhancer or thickener in an amount from about 0.1 wt-%to about 5 wt-%, an additional surfactant in an amount from about 0.01wt-% to about 50 wt-%, a sequestrant in an amount from about 0.01 wt-%to about 50 wt-%, and a solidification agent in an amount from about0.01 wt-% to about 50 wt-%.

In some aspects, the antimicrobial compositions or inactivatedantimicrobial compositions according to the invention may comprise,consist of and/or consist essentially of a quaternary ammonium compoundin an amount from about 0.001 wt-% to about 75 wt-%, an anionicsurfactant or anionic polymer/chelant in an amount from about 0.0001wt-% to about 50 wt-%, and at least one additional functional ingredientselected from the group consisting of: additional surfactants,thickeners and/or viscosity modifiers, solvents, solubility modifiers,humectants, metal protecting agents, corrosion inhibitors, sequestrantsand/or chelating agents, solidifying agent, sheeting agents, pHmodifying components, including alkalinity and/or acidity sources,aesthetic enhancing agents (i.e., colorants, odorants, or perfumes),other cleaning agents, hydrotropes or couplers, buffers, and the like inan amount from about 0.01 wt-% to about 50 wt-%.

In some aspects, the antimicrobial compositions or inactivatedantimicrobial compositions according to the invention may comprise,consist of and/or consist essentially of a quaternary ammonium compoundin an amount from about 0.001 wt-% to about 75 wt-%, an anionicsurfactant or anionic polymer/chelant in an amount from about 0.0001wt-% to about 50 wt-%, and at least two additional functionalingredients selected from the group consisting of: additionalsurfactants, thickeners and/or viscosity modifiers, solvents, solubilitymodifiers, humectants, metal protecting agents, corrosion inhibitors,sequestrants and/or chelating agents, solidifying agent, sheetingagents, pH modifying components, including alkalinity and/or aciditysources, aesthetic enhancing agents (i.e., colorants, odorants, orperfumes), other cleaning agents, hydrotropes or couplers, buffers, andthe like in an amount from about 0.01 wt-% to about 50 wt-%.

In some aspects, the antimicrobial compositions or inactivatedantimicrobial compositions according to the invention may comprise,consist of and/or consist essentially of a quaternary ammonium compoundin an amount from about 0.001 wt-% to about 75 wt-%, an anionicsurfactant or anionic polymer/chelant in an amount from about 0.0001wt-% to about 50 wt-%, and at least three additional functionalingredients selected from the group consisting of: additionalsurfactants, thickeners and/or viscosity modifiers, solvents, solubilitymodifiers, humectants, metal protecting agents, corrosion inhibitors,sequestrants and/or chelating agents, solidifying agent, sheetingagents, pH modifying components, including alkalinity and/or aciditysources, aesthetic enhancing agents (i.e., colorants, odorants, orperfumes), other cleaning agents, hydrotropes or couplers, buffers, andthe like in an amount from about 0.01 wt-% to about 50 wt-%.

In some aspects, the antimicrobial compositions or inactivatedantimicrobial compositions according to the invention may comprise,consist of and/or consist essentially of a quaternary ammonium compoundin an amount from about 0.001 wt-% to about 75 wt-%, an anionicsurfactant or anionic polymer/chelant in an amount from about 0.0001wt-% to about 50 wt-%, and at least four additional functionalingredients selected from the group consisting of: additionalsurfactants, thickeners and/or viscosity modifiers, solvents, solubilitymodifiers, humectants, metal protecting agents, corrosion inhibitors,sequestrants and/or chelating agents, solidifying agent, sheetingagents, pH modifying components, including alkalinity and/or aciditysources, aesthetic enhancing agents (i.e., colorants, odorants, orperfumes), other cleaning agents, hydrotropes or couplers, buffers, andthe like in an amount from about 0.01 wt-% to about 50 wt-%.

In some aspects, the antimicrobial compositions or inactivatedantimicrobial compositions according to the invention may comprise,consist of and/or consist essentially of a quaternary ammonium compoundin an amount from about 0.001 wt-% to about 75 wt-%, an anionicsurfactant or anionic polymer/chelant in an amount from about 0.0001wt-% to about 50 wt-%, and at least five additional functionalingredients selected from the group consisting of: additionalsurfactants, thickeners and/or viscosity modifiers, solvents, solubilitymodifiers, humectants, metal protecting agents, corrosion inhibitors,sequestrants and/or chelating agents, solidifying agent, sheetingagents, pH modifying components, including alkalinity and/or aciditysources, aesthetic enhancing agents (i.e., colorants, odorants, orperfumes), other cleaning agents, hydrotropes or couplers, buffers, andthe like in an amount from about 0.01 wt-% to about 50 wt-%.

Solubilizing Fatty Acids

A method of solubilizing a fatty acid is included. In an exemplaryapplication, solubilizing a fatty acid is particularly useful for thesolubilization and therefore removal of a fatty acid soil (cohesiveenergy). The method includes providing a carboxylic fatty acid andsolubilizing it with a quaternary ammonium. Such method results in acomposition having heightened antimicrobial activities. In an embodimenta mole: mole ratio of fatty acid to quaternary ammonium compound is usedto solubilize the fatty acid. In a further embodiment, the solubilizingof a fatty acid includes approximately a mole to mole ratio ofquaternary ammonium compound and fatty acid. In other aspects, thecompositions include up to about a 10 to about a 1 molar ratio ofquaternary ammonium compound and fatty acid. In other aspects, thecompositions include up to about 1 to about a 10 molar ratio ofquaternary ammonium compound and fatty acid, or any combination thereofIn another embodiment the compositions are provided with a molar ratioof fatty acid to quaternary ammonium of about 1 mole fatty acid to about1 mole of quaternary ammonium compound. In another embodiment thecomposition is provided with a molar ratio of fatty acid to quaternaryammonium compound of about 1.5 mole fatty acid to about 1 mole ofquaternary ammonium compound. In another embodiment the composition isprovided with a molar ratio of fatty acid to quaternary ammoniumcompound of about 1 mole fatty acid to about 10 moles of quaternaryammonium compound. In another embodiment the composition is providedwith a molar ratio of fatty acid to quaternary ammonium compound ofabout 2 moles fatty acid to about 1 mole of quaternary ammoniumcompound.

Without being limited to a particular mechanism of action, when it issaid that the fatty acid is solubilized it is meant that the combinationincluding the fatty acid is soluble in water. A composition is said tobe “water soluble” if it is at least 90 percent soluble in water, atleast 95 percent soluble in water, at least 98 percent soluble in water,at least 99 percent soluble in water, and at least 99.9 percent solublein water.

Use Compositions

The activated antimicrobial compositions and inactivated compositions ofthe present invention may include concentrate compositions and usecompositions, or may be diluted to form use compositions. For example, aconcentrate composition can be diluted, for example with water, to forma use composition. In general, a concentrate refers to a compositionthat is intended to be diluted, such as with water to provide a usesolution that contacts a surface and/or product in need of treatment toprovide the desired surface activity. The antimicrobial compositions orinactivated antimicrobial compositions that contact the surface and/orproduct in need of treatment can be referred to as a concentrate or ause composition (or use solution) dependent upon the formulationemployed in methods according to the invention. It should be understoodthat the concentration of the quaternary ammonium compound and anionicsurfactants in the composition will vary depending on whether thecomposition is provided as a concentrate or as a use solution. In anembodiment, a concentrate composition can be diluted to a use solutionbefore applying to an object. The concentrate can be marketed and an enduser can dilute the concentrate with water or an aqueous diluent to ause solution.

Compositions of the invention can be formulated and sold for use as is,or as solvent concentrates. If desired, such concentrates can be usedfull-strength as antimicrobial agents. However, the concentratestypically will be diluted with a fluid (e.g., water) that subsequentlyforms the dilute phase or a use solution. Preferably, the concentrateforms a single phase before such dilution and remains so while stored inthe container in which it will be sold. When combined with water orother desired diluting fluid at an appropriate dilution level andsubjected to mild agitation (e.g., by stirring or pumping thecomposition), some compositions of the invention will form apseudo-stable dispersion, and other compositions of the invention willform a clear or quasi-stable solution or dispersion. If a pseudo-stablecomposition is formed, then the composition preferably remains in thepseudo-stable state for a sufficiently long period so that thecomposition can be applied to a surface before the onset of phaseseparation. The pseudo-stable state need only last for a few secondswhen suitably rapid application techniques such as spraying areemployed, or when agitation during application is employed. Thepseudo-stable state desirably lasts for at least one minute or moreafter mixing and while the composition is stored in a suitable vessel,and preferably lasts for five minutes or more after mixing. Often normalrefilling or replenishment of the applicator (e.g., by dipping theapplicator in the composition) will provide sufficient agitation topreserve the pseudo-stable state of the composition during application.

A use solution may be prepared from the concentrate by diluting theconcentrate with water at a dilution ratio that provides a use solutionhaving desired sanitizing and/or other antimicrobial properties. Thewater that is used to dilute the concentrate to form the use compositioncan be referred to as water of dilution or a diluent, and can vary fromone location to another. The typical dilution factor is betweenapproximately 1 and approximately 10,000 but will depend on factorsincluding water hardness, the amount of soil to be removed and the like.In an embodiment, the concentrate is diluted at a ratio of between about1:10 and about 1:10,000 concentrate to water. Particularly, theconcentrate is diluted at a ratio of between about 1:100 and about1:5,000 concentrate to water. More particularly, the concentrate isdiluted at a ratio of between about 1:250 and about 1:2,000 concentrateto water.

In preferred embodiments the present invention includes concentratecompositions and use compositions. In an embodiment, a concentratecomposition can be diluted to a use solution before applying to anobject. The concentrate can be marketed and an end user can dilute theconcentrate with water or an aqueous diluent to a use solution. Thelevel of active components in the concentrate composition is dependenton the intended dilution factor and the desired activity of theantimicrobial composition. Generally, a dilution of about 1 fluid ounceto about 10 gallons of water to about 10 fluid ounces to about 1 gallonof water is used for aqueous compositions of the present invention. Insome embodiments, higher use dilutions can be employed if elevated usetemperature (greater than 25° C.) or extended exposure time (greaterthan 30 seconds) can be employed. In the typical use locus, theconcentrate is diluted with a major proportion of water using commonlyavailable tap or service water mixing the materials at a dilution ratioof about 3 to about 40 ounces of concentrate per 100 gallons of water.

In some embodiments, the concentrated compositions can be diluted at adilution ratio of about 0.1 g/L to about 100 g/L concentrate to diluent,about 0.5 g/L to about 10.0 g/L concentrate to diluent, about 1.0 g/L toabout 4.0 g/L concentrate to diluent, or about 1.0 g/L to about 2.0 g/Lconcentrate to diluent.

In other embodiments, a use composition can include about 0.01 to about10 wt-% of a concentrate composition and about 90 to about 99.99 wt-%diluent; or about 0.1 to about 1 wt-% of a concentrate composition andabout 99 to about 99.9 wt-% diluent.

Amounts of an ingredient in a use composition can be calculated from theamounts listed above for concentrate compositions and these dilutionfactors. In some embodiments, the concentrated compositions of thepresent invention are diluted such that the quaternary ammoniumcomponent is present at from about 10 ppm to about 100 ppm, or about 50ppm to about 400 ppm. In other embodiments, the concentratedcompositions of the present invention are diluted such that thequaternary ammonium component is present at about 20 ppm or more, about40 ppm or more, about 60 ppm or more, about 80 ppm or more, about 100ppm or more, about 500 ppm, about 1000 ppm, or about 10,000 to about20,000 ppm. It is to be understood that all values and ranges betweenthese values and ranges are encompassed by the present invention.

A variety of fluids can be used as the diluting solvent, including waterin its liquid form; steam; condensed gases and other supercriticalfluids (e.g., CO₂); perchloroethylene; oils such as silicone oils (e.g.,siloxanes), gear oils, transaxle oils, mineral oils or vegetable oils;and carboxylic esters such as methyl soyate. Mixtures of dilutingsolvents can be used if desired. Preferably, the diluting solventconsists essentially of or consists of water in its liquid form. Theremainder of this specification will primarily discuss the use of waterin its liquid form as the diluting solvent, it being understood thatother suitable fluids could be added to or substituted for water in itsliquid form if desired.

In an embodiment of the invention, the concentrated compositions and usecompositions maintain their sanitizing efficacy while being tolerant towater conditions, or are independent of water conditions such as waterhardness. According to embodiments of the invention, compositions aretolerant of water conditions of about 0 parts per million (ppm) to about500 ppm (about 0 to about 30 grains per gallon) water hardness withoutimpacting sanitizing efficacy according to embodiments of the invention.As referred to herein, the ppm of water hardness refers to ppm ofcalcium, magnesium and other metals which may be found in the water andcontributing to the hardness level.

Manufacturing Methods

Compositions of the invention are prepared by addition of materials. Theanionic surfactant is added to the quaternary ammonium. The quaternaryammonium compound readily couples the more hydrophobic organic acid intosolution with minimal or no agitation.

In an aspect, the addition of materials is provided in a mole to moleratio of quaternary ammonium and anionic surfactant up to about a 10:about 1 molar ratio. In an embodiment the ratio of quaternary ammoniumto anionic surfactant is about mole to mole.

In some aspects, the compositions according to the invention can be madeby combining the components in an aqueous diluent using commonlyavailable containers and blending apparatus. Beneficially, no specialmanufacturing equipment is required for making the compositionsemploying the quaternary ammonium compounds and the anionic surfactants.A preferred method for manufacturing the cleaning composition of theinvention includes introducing the components into a stirred productionvessel.

The antimicrobial compositions and/or inactivated antimicrobialcompositions according to the invention can be provided in single use ormultiple use compositions. In a preferred aspect, the composition is aconcentrated liquid or solid composition. Various solids can be employedaccording to the invention and without limiting the scope of theinvention. It should be understood that compositions and methodsembodying the invention are suitable for preparing a variety of solidcompositions, as for example, a cast, extruded, pressed, molded orformed solid pellet, block, tablet, and the like. In some embodiments,the solid composition can be formed to have a weight of 50 grams orless, while in other embodiments, the solid composition can be formed tohave a weight of 50 grams or greater, 500 grams or greater, or 1kilogram or greater.

Methods Employing Antimicrobial Compositions of the Invention

The present invention includes methods of using the antimicrobialcompositions of the present invention for various applications. Theinvention includes a method for reducing a microbial population, amethod for reducing the population of a microorganism on skin and amethod for treating a disease of skin. These methods can operate on anarticle, surface, in a body or stream of water or a gas, or the like, bycontacting the article, surface, body, or stream with a composition ofthe invention. Contacting can include any of numerous methods forapplying a composition of the invention, such as spraying thecompositions, immersing the article in compositions, foam or geltreating the article with the compounds or composition, or a combinationthereof.

In some embodiments, the compositions of the present invention includekilling one or more of the pathogenic bacteria associated with healthcare surfaces and environments including, but not limited to, Salmonellatyphimurium, Staphylococcus aureus, methicillin resistant Staphylococcusaureus, Salmonella choleraesurus, Pseudomonas aeruginosa, Escherichiacoli, mycobacteria, yeast, and mold. The compositions of the inventionhave activity against a wide variety of microorganisms such as Grampositive (for example, Listeria monocytogenes or Staphylococcus aureus)and Gram negative (for example, Escherichia coli or Pseudomonasaeruginosa) bacteria, yeast, molds, bacterial spores, viruses, etc. Thecompounds and compositions of the present invention, as described above,have activity against a wide variety of human pathogens. The presentcompounds and compositions can kill a wide variety of microorganisms ona food processing surface, on the surface of a food product, in waterused for washing or processing of food product, on a health caresurface, or in a health care environment.

The present methods can be used to achieve any suitable reduction of themicrobial population in and/or on the target or the treated targetcomposition. In some embodiments, the present methods can be used toreduce the microbial population in and/or on the target or the treatedtarget composition by at least one log10. In other embodiments, thepresent methods can be used to reduce the microbial population in and/oron the target or the treated target composition by at least two log10.In still other embodiments, the present methods can be used to reducethe microbial population in and/or on the target or the treated targetcomposition by at least three log10. In still other embodiments, thepresent methods can be used to reduce the microbial population in and/oron the target or the treated target composition by at least five log10.Without limiting the scope of invention, the numeric ranges areinclusive of the numbers defining the range and include each integerwithin the defined range.

The compositions of the invention can be used for a variety of domesticor industrial applications, e.g., to reduce microbial or viralpopulations on a surface or object or in a body or stream of water. Thecompounds can be applied in a variety of areas including kitchens,bathrooms, factories, hospitals, dental offices and food plants, and canbe applied to a variety of hard or soft surfaces having smooth,irregular or porous topography. Suitable hard surfaces include, forexample, architectural surfaces (e.g., floors, walls, windows, sinks,tables, counters and signs); eating utensils; hard-surface medical orsurgical instruments and devices; and hard-surface packaging. Such hardsurfaces can be made from a variety of materials including, for example,ceramic, metal, glass, wood or hard plastic. Suitable soft surfacesinclude, for example paper; filter media; hospital and surgical linensand garments; soft-surface medical or surgical instruments and devices;and soft-surface packaging. Such soft surfaces can be made from avariety of materials including, for example, paper, fiber, woven ornonwoven fabric, soft plastics and elastomers. The compositions of theinvention can also be applied to soft surfaces such as food and skin(e.g., a hand). The present compounds can be employed as a foaming ornon-foaming environmental sanitizer or disinfectant.

The compositions of the invention can be included in products such assterilants, sanitizers, disinfectants, preservatives, deodorizers,antiseptics, fungicides, germicides, sporicides, virucides, detergents,bleaches, hard surface cleaners, hand soaps, waterless hand sanitizers,lubricants, rinse aids, 2-in-1 and/or 3-in-1 products, such asinsecticide/cleaner/sanitizer, 3-sink applications, and pre- orpost-surgical scrubs.

The compositions can also be used in veterinary products such asmammalian skin treatments or in products for sanitizing or disinfectinganimal enclosures, pens, watering stations, and veterinary treatmentareas such as inspection tables and operation rooms. The presentcompositions can be employed in an antimicrobial foot bath for livestockor people.

In some aspects, the compositions of the present invention can beemployed for reducing the population of pathogenic microorganisms, suchas pathogens of humans, animals, and the like. The compounds exhibitactivity against pathogens including fungi, molds, bacteria, spores, andviruses, for example, S. aureus, E. coli, Streptococci, Legionella,Pseudomonas aeruginosa, mycobacteria, tuberculosis, phages, or the like.Such pathogens can cause a variety of diseases and disorders, includingmastitis or other mammalian milking diseases, tuberculosis, and thelike. Compositions of the present invention can reduce the population ofmicroorganisms on skin or other external or mucosal surfaces of ananimal. In addition, the present compounds can kill pathogenicmicroorganisms that spread through transfer by water, air, or a surfacesubstrate. The compositions need only be applied to the skin, otherexternal or mucosal surfaces of an animal water, air, or surface.

The antimicrobial compositions can also be used on foods and plantspecies to reduce surface microbial populations; used at manufacturingor processing sites handling such foods and plant species; or used totreat process waters around such sites. For example, the compounds canbe used on food transport lines (e.g., as belt sprays); boot andhand-wash dip-pans; food storage facilities; anti-spoilage aircirculation systems; refrigeration and cooler equipment; beveragechillers and warmers, blanchers, cutting boards, third sink areas, andmeat chillers or scalding devices. The compositions of the invention canbe used to treat produce transport waters such as those found in flumes,pipe transports, cutters, slicers, blanchers, retort systems, washers,and the like. Particular foodstuffs that can be treated with compoundsof the invention include eggs, meats, seeds, leaves, fruits andvegetables. Particular plant surfaces include both harvested and growingleaves, roots, seeds, skins or shells, stems, stalks, tubers, corms,fruit, and the like.

In some aspects, the compositions of the present invention are useful inthe cleaning or sanitizing of containers, processing facilities, orequipment in the food service or food processing industries. Thecompositions have particular value for use on food packaging materialsand equipment, and especially for cold or hot aseptic packaging.Examples of process facilities in which the compound of the inventioncan be employed include a milk line dairy, a continuous brewing system,food processing lines such as pumpable food systems and beverage lines,etc. Food service wares can be disinfected with the compound of theinvention. For example, the compounds can also be used on or in warewash machines, low temperature ware wash machines, dishware, bottlewashers, bottle chillers, warmers, third sink washers, cutting areas(e.g., water knives, slicers, cutters and saws) and egg washers.Particular treatable surfaces include packaging such as cartons,bottles, films and resins; dish ware such as glasses, plates, utensils,pots and pans; ware wash and low temperature ware wash machines; exposedfood preparation area surfaces such as sinks, counters, tables, floorsand walls; processing equipment such as tanks, vats, lines, pumps andhoses (e.g., dairy processing equipment for processing milk, cheese, icecream and other dairy products); and transportation vehicles. Containersinclude glass bottles, PVC or polyolefin film sacks, cans, polyester,PEN or PET bottles of various volumes (100 ml to 2 liters, etc.), onegallon milk containers, paper board juice or milk containers, etc.

Compositions of the present invention can also be employed by dippingfood processing equipment into the use solution, soaking the equipmentfor a time sufficient to sanitize the equipment, and wiping or drainingexcess solution off the equipment, The compound may be further employedby spraying or wiping food processing surfaces with the use solution,keeping the surfaces wet for a time sufficient to sanitize the surfaces,and removing excess solution by wiping, draining vertically, vacuuming,etc.

Compositions of the present invention may also be used in a method ofsanitizing hard surfaces such as institutional type equipment, utensils,dishes, health care equipment or tools, instruments and other hardsurfaces.

The antimicrobial compositions can be applied to microbes or to soiledor cleaned surfaces using a variety of methods. These methods canoperate on an object, surface, in a body or stream of water or a gas, orthe like, by contacting the object, surface, body, or stream with acompound of the invention. Contacting can include any of numerousmethods for applying a compound, such as spraying the compound,immersing the object in the compound, foam or gel treating the objectwith the compound, or a combination thereof.

A concentrate or use concentration of a compound of the presentinvention can be applied to or brought into contact with an object byany conventional method or apparatus for applying an antimicrobial orcleaning compound to an object. For example, the object can be wipedwith, sprayed with, foamed on, and/or immersed in the compound, or a usesolution made from the composition. The composition can be sprayed,foamed, or wiped onto a surface; the composition can be caused to flowover the surface, or the surface can be dipped into the composition.Contacting can be manual or by machine. Food processing surfaces, foodproducts, food processing or transport waters, and the like can betreated with liquid, foam, gel, aerosol, gas, wax, solid, or powderedstabilized compounds according to the invention, or solutions containingthese compounds.

The various methods of treatment according to the invention can includethe use of any suitable level of the quaternary ammonium compound andanionic surfactant. In some embodiments, the treated target compositioncomprises from about 1 ppm to about 1000 ppm of the quaternary ammoniumcompound when diluted for use. In further embodiments, the treatedtarget composition comprises from about 1 ppm and about 500 ppm, 5 ppmand about 400 ppm, 10 ppm and about 100 ppm, 20 ppm and about 100 ppm,25 ppm and about 100 ppm, 10 ppm and about 75 ppm, 20 ppm and about 75ppm, 25 ppm and about 75 ppm, or about 50 ppm of the quaternary ammoniumcompound when diluted for use. In some embodiments, the treated targetcomposition comprises from about 1 ppm to about 1000 ppm of the anionicsurfactant in a use solution. In further embodiments, the treated targetcomposition comprises from about 1 ppm and about 500 ppm, 5 ppm andabout 250 ppm, 10 ppm and about 100 ppm, 20 ppm and about 100 ppm, 25ppm and about 100 ppm, 10 ppm and about 50 ppm, 20 ppm and about 50 ppm,25 ppm and about 50 ppm, or about 50 ppm and about 100 ppm of theanionic surfactant when diluted for use.

In an aspect, the methods of the invention include generating a usesolution from the concentrated solid or liquid compositions of theinvention. A use solution may be prepared from the concentrate bydiluting the concentrate with water at a dilution ratio that provides ause solution having desired sanitizing and/or other antimicrobialproperties. The water that is used to dilute the concentrate to form theuse composition can be referred to as water of dilution or a diluent,and can vary from one location to another. The typical dilution factoris between approximately 1 and approximately 10,000. In an embodiment,the concentrate is diluted at a ratio of between about 1:10 and about1:10,000 concentrate to water. Particularly, the concentrate is dilutedat a ratio of between about 1:100 and about 1:5,000 concentrate towater. More particularly, the concentrate is diluted at a ratio ofbetween about 1:250 and about 1:2,000 concentrate to water.

In an aspect, a concentrated antimicrobial composition is diluted to usesolution concentration of about 0.001% (wt/vol.) to about 10% (wt/vol.),or from about 0.001% (wt/vol.) to about 5% (wt/vol.), or from about0.001% (wt/vol.) to about 2% (wt/vol.), or from about 0.01% (wt/vol.) toabout 1% (wt/vol.). Without limiting the scope of invention, the numericranges are inclusive of the numbers defining the range and include eachinteger within the defined range.

Compositions of the invention can be formulated and sold for use as is,or as solvent or solid concentrates. If desired, such concentrates canbe used full-strength as sanitizing rinse compositions. However, theconcentrates typically will be diluted with a fluid (e.g., water) thatsubsequently forms the dilute phase or a use solution. Preferably, theconcentrate forms a single phase before such dilution and remains sowhile stored in the container in which it will be sold. When combinedwith water or other desired diluting fluid at an appropriate dilutionlevel and subjected to mild agitation (e.g., by stirring or pumping thecomposition), some compositions of the invention will form apseudo-stable dispersion, and other compositions of the invention willform a clear or quasi-stable solution or dispersion. If a pseudo-stablecomposition is formed, then the composition preferably remains in thepseudo-stable state for a sufficiently long period so that thecomposition can be applied to a surface before the onset of phaseseparation. The pseudo-stable state need only last for a few secondswhen suitably rapid application techniques such as spraying areemployed, or when agitation during application is employed. Thepseudo-stable state desirably lasts for at least one minute or moreafter mixing and while the composition is stored in a suitable vessel,and preferably lasts for five minutes or more after mixing. Often normalrefilling or replenishment of the applicator (e.g., by dipping theapplicator in the composition) will provide sufficient agitation topreserve the pseudo-stable state of the composition during application.

The various applications of use described herein provide the quaternaryammonium compound and anionic surfactant compositions to a surfaceand/or water source. Beneficially, the compositions of the invention arefast-acting. However, the present methods require a certain minimalcontact time of the compositions with the surface or product in need oftreatment for occurrence of sufficient antimicrobial effect. The contacttime can vary with concentration of the use compositions, method ofapplying the use compositions, temperature of the use compositions, pHof the use compositions, amount of the surface or product to be treated,amount of soil or substrates on/in the surface or product to be treated,or the like. The contact or exposure time can be about 15 seconds, atleast about 15 seconds, about 30 seconds or greater than 30 seconds. Insome embodiments, the exposure time is about 1 to 5 minutes. In otherembodiments, the exposure time is a few minutes to hours. In otherembodiments, the exposure time is a few hours to days. The contact timewill further vary based upon the use concentration of actives ofcompositions according to the invention.

Scale/Mineral Removal

The activated quaternary ammonium compound and anionic surfactant (orpolymer/chelant) compositions of the invention are further suitable foruse in various applications and methods in need of treating orpreventing scaling, including hard water/mineral scale control onsurfaces. In a preferred embodiment, the anionic polymer or chelantprovides a surface active material suitable for concentrating at aninterface to provide beneficial scale mineral removal. In addition, themethods of the invention are well suited for controlling water hardnessbuildup on a plurality of surfaces. The methods of the invention preventmoderate to heavy accumulation of hardness and/or the redeposition ofsoils on treated substrate surfaces which beneficially improving theaesthetic appearance of the surface. In certain embodiments, surfaces inneed of hard water scale accumulation prevention, include for example,plastics, metal and/or glass surfaces.

In a beneficial aspect of the invention, the methods of the inventionreduce the formation, precipitation and/or deposition of hard waterscale, such as calcium carbonate, on hard surfaces contacted by theactivated compositions. In an embodiment, the activated compositions areemployed for the prevention of formation, precipitation and/ordeposition of hard water scale on articles such as glasses, plates,silverware, etc. The activated compositions are effective at removingand/or preventing hard water scale accumulation and/or preventing theredeposition of soils in various applications, such as warewashingapplications, using a variety of water sources, including hard water. Inaddition, the activated compositions are suitable for use at temperatureranges typically used in industrial warewashing applications, includingfor example from about 150° F. to about 165° F. during washing steps andfrom about 170° F. to about 185° F. during rinsing steps.

In addition, the methods of use of the activated compositions accordingto the present invention are also suitable for CIP and/or COP processesto replace the use of bulk detergents leaving hard water residues ontreated surfaces. The methods of use may be desirable in additionalapplications where industrial standards are focused on the quality ofthe treated surface, such that the prevention of hard water scaleaccumulation provided by the activated compositions of the invention aredesirable. Such applications may include, but are not limited to,vehicle care, industrial, hospital and textile care.

Additional examples of applications of use for the activatedcompositions include, for example, alkaline detergents effective asgrill and oven cleaners, ware wash detergents, laundry detergents,laundry presoaks, drain cleaners, hard surface cleaners, surgicalinstrument cleaners, transportation vehicle cleaning, vehicle cleaners,dish wash presoaks, dish wash detergents, beverage machine cleaners,concrete cleaners, building exterior cleaners, metal cleaners, floorfinish strippers, degreasers and burned-on soil removers. In a varietyof these applications, cleaning compositions having a very highalkalinity are most desirable and efficacious; however, the damagecaused by hard water scale accumulation is undesirable.

In general, the various applications of use can be employed by dipping,spraying, submerging or otherwise contacting the surface with a usesolution for a time sufficient, including from a few seconds to a fewminutes, or longer. The methods may further include wiping or drainingexcess solution from the surface.

Destaining

The activated quaternary ammonium compound and anionic surfactant (orpolymer/chelant) compositions of the invention are further suitable foruse in various applications and methods in need of destaining. Ingeneral, the compositions can be used for destaining by dipping,spraying, submerging or otherwise contacting the surface with a usesolution for a time sufficient, including from a few seconds to a fewminutes, or longer and wiping or draining excess solution off theequipment. The compositions of the present invention may be furtheremployed by spraying or wiping food processing surfaces with the usesolution, keeping the surfaces wet for a time sufficient to sanitize thesurfaces, and removing excess solution by wiping, draining vertically,vacuuming, etc.

The activate compositions obtained according to the present inventionmay also be used in a method of destaining various hard surfaces such asinstitutional type equipment, utensils, dishes, health care equipment ortools, and other hard surfaces.

Laundry Applications

In some aspects, the compounds and compositions can also be employed insanitizing articles, e.g., textiles, which have become contaminated. Infurther aspects, the compounds and compositions can also be employed incleaning and disinfecting articles, e.g., textiles. The articles arecontacted with the compounds of the invention at use temperatures in therange of about 4° C. to 80° C., for a period of time effective tosanitize, disinfect, and/or sterilize the articles. In some embodiments,the compositions of the present invention can be used to sanitizearticles at a temperature of about 30° C. to about 50° C. or about 40°C. For example, in some embodiments, the compositions of the presentinvention can be injected into the wash or rinse water of a laundrymachine and contacted with contaminated fabric for a time sufficient tosanitize the fabric. In some embodiments, the contaminated fabric iscontacted with the compounds and compositions of the present inventionfor about 5 to about 30 minutes. Excess solution can then be removed byrinsing or centrifuging the fabric.

The compositions of the present invention can be used alone to treat thearticles, e.g., textiles, or can be used in conjunction withconventional detergents suitable for the articles to be treated. Thecompositions of the invention can be used with conventional detergentsin a variety of ways, for example, the compositions of the invention canbe formulated with a conventional detergent. In other embodiments, thecompositions of the invention can be used to treat the article as aseparate additive from a conventional detergent. When used as a separateadditive, the compounds and compositions of the present invention cancontact the article to be treated at any time. For example, thecompositions of the invention can contact the article before, after, orsubstantially simultaneously as the articles are contacted with theselected detergent.

In some embodiments, when used as a sanitizing/disinfecting agent for alaundry application, compounds of the present invention will be presentin a composition at about 5 ppm to about 1000 ppm. In other embodiments,when used as a sanitizing/disinfecting agent for a laundry application,a compound or mixture of compounds of the present invention will bepresent in a composition at about 25 ppm to about 100 ppm. In otherembodiments, when used as a sanitizing/disinfecting agent in a laundryapplication, a compound or mixture thereof of the present invention willbe present at about 20, about 40, about 60, or about 80 ppm.

Methods Employing Inactivated Antimicrobial Compositions of theInvention Water Treatment Applications

The inactivated compositions can be used for a variety of purposes,including for example treating water sources and water treatmentapplications. In various applications, water sources and waste sourcescontain residual antimicrobial agents, including quaternary ammoniumcompounds.

In an embodiment, the inactivated compositions can be utilized for watertreatment methods connected to a water main of a house or business. Theinactivated compositions can be employed in line before the hot waterheater, or after the hot water heater. In other aspects, the presentinvention provides inactivated compositions for use in a cleaningprocess.

In other embodiments once the water has been treated, the treated wateris provided to an automatic washing machine, e.g., an automatic warewashing or dishwashing machine, a vehicle washing system, an instrumentwasher, a clean in place system, a food processing cleaning system, abottle washer, and an automatic laundry washing machine, from thetreated water delivery line of the apparatus. Alternatively, the treatedwater may be used in a manual washing system. Any automatic or manualwashing machine that would benefit from the use of water treated inaccordance with the methods of the present invention can be used. Thetreated water is then combined with a detersive composition in thewashing machine to provide a use composition. Any detersive compositioncan be used in the system of the present invention, for example, acleaning composition, a rinse agent composition or a drying agentcomposition. The articles to be cleaned are then contacted with the usesolution in the automatic washing machine such that they are cleaned.

The water treatment methods and systems of the present invention can beused in a variety of industrial and domestic applications. The watertreatment methods and systems can be employed in a residential settingor in a commercial setting, e.g., in a restaurant, hotel, hospital. Forexample, a water treatment method, system, or apparatus of the presentinvention can be used in: ware washing applications, e.g., washingeating and cooking utensils and other hard surfaces such as showers,sinks, toilets, bathtubs, countertops, windows, mirrors, and floors; inlaundry applications, e.g., to treat water used in an automatic textilewashing machine at the pre-treatment, washing, souring, softening,and/or rinsing stages; in vehicle care applications, e.g., to treatwater used for pre-rinsing, e.g., an alkaline presoak and/or low pHpresoak, washing, polishing, and rinsing a vehicle; industrialapplications, e.g., cooling towers, boilers, industrial equipmentincluding heat exchangers; in food service applications, e.g., to treatwater lines for coffee and tea brewers, espresso machines, ice machines,pasta cookers, water heaters, steamers and/or proofers; in healthcareinstrument care applications, e.g., soaking, cleaning, and/or rinsingsurgical instruments, treating feedwater to autoclave sterilizers; andin feedwater for various applications such as humidifiers, hot tubs, andswimming pools

In some embodiments, the water treatment methods can be applied at thepoint of use. That is, a water treatment method, system, or apparatuscan be applied to a water source upstream of an application such as awashing system. In some embodiments, the water treatment is appliedimmediately prior to the desired end use of the water source. Forexample, an apparatus of the present invention could be employed to awater line connected to a household or restaurant appliance, e.g., acoffee maker, an espresso machine, an ice machine. An apparatusemploying the methods of the present invention may be located in awashing system. For example, it can also be included as part of anappliance which uses a water source, e.g., a water treatment systembuilt into an automatic or manual washing system, a coffee maker, an icemachine, or any other system which may benefit from the use of treatedwater.

In various applications the anionic surfactants disclosed according tothe invention can be dosed directly to the water sources or wastesources which comprise residual quaternary ammonium compounds. Theapplication of the anionic surfactants according to the invention can beutilized to inactivate the quaternary ammonium compounds in the watersource or waste streams, which could otherwise negatively interfere withor disrupt bacteria or other compounds therein. Accordingly, it can bedesired to inactivate the quaternary ammonium compounds in the watersource or waste streams with an in situ inactivation of theantimicrobial compositions.

Kits for Applications of Use

According to various applications of the compositions according to theinvention a kit may be provided for dosing a composition according tothe invention, including either inactivating or activating a quaternaryammonium composition. In a particular application, the inactivatedcompositions may be provided by employing a kit according to embodimentsof the invention. A kit for dosing and/or providing an inactivatingquaternary ammonium composition according to the invention may comprise,consist of and/or consist essentially of a quaternary ammonium compoundand an anionic surfactant (and/or chelant and/or polymer).Alternatively, the kits may comprise, consist of and/or consistessentially of an anionic surfactant (and/or chelant and/or polymer) fordosing with a quaternary ammonium compound in an application of use. Thekit may further comprise a measuring means and/or a dosing means.

In an aspect, a kit is employed for the dosing of a suitable amount ofan anionic surfactant (and/or chelant and/or polymer) to inactivate aquaternary ammonium compound. In an aspect, it may be desirable to doseor provide a surface and/or antimicrobial-inactivating amount of theanionic surfactant (and/or chelant and/or polymer). In embodiments it isdesirable to lower surface activity (higher surface tension) as comparedto another combination of anionic surfactant (and/or chelant and/orpolymer) and a quaternary ammonium compound, such that the low surfaceactivity neutralizes or deactivates the antimicrobial efficacy of thequaternary ammonium compound.

According to some embodiments of employing a kit, a composition and/orsystem having a quaternary ammonium compound is dosed a molar ratiodependent amount of the anionic surfactant (and/or chelant and/orpolymer). In an aspect, the compositions include approximately a mole tomole ratio of quaternary ammonium compound and anionic surfactant. Inother aspects, the compositions include up to about a 10 to about a 1molar ratio of quaternary ammonium compound and anionic surfactant. Inother aspects, the compositions include up to about 1 to about a 10molar ratio of quaternary ammonium compound and anionic surfactant, orany combination thereof. In another embodiment the antimicrobialcompositions are provided with a molar ratio of anionic surfactant toquaternary ammonium of about 1 mole anionic surfactant to about 1 moleof quaternary ammonium compound. In another embodiment the antimicrobialcomposition is provided with a molar ratio of anionic surfactant toquaternary ammonium compound of about 1.5 mole anionic surfactant toabout 1 mole of quaternary ammonium compound. In another embodiment theantimicrobial composition is provided with a molar ratio of anionicsurfactant to quaternary ammonium compound of about 1 mole anionicsurfactant to about 10 moles of quaternary ammonium compound. In anotherembodiment the antimicrobial composition is provided with a molar ratioof anionic surfactant to quaternary ammonium compound of about 2 molesanionic surfactant to about 1 mole of quaternary ammonium compound. Ineach embodiment, the kit provides the mole ratio to inactivate thequaternary ammonium compound.

The kit may further comprise additional elements. For example, a kit mayalso include instructions for use of the inactivated compositions.Instructions included in kits can be affixed to packaging material orcan be included as a package insert. While the instructions aretypically written or printed materials they are not limited to such. Anymedium capable of storing such instructions and communicating them to anend user is contemplated by this disclosure. Such media include, but arenot limited to, electronic storage media (e.g., magnetic discs, tapes,cartridges, chips), optical media (e.g., CD, DVD), and the like. As usedherein, the term “instructions” can include the address of an internetsite that provides the instructions. The various components of the kitoptionally are provided in suitable containers as necessary, e.g., abottle, jar or vial.

EXAMPLES

Embodiments of the present invention are further defined in thefollowing non-limiting Examples. It should be understood that theseExamples, while indicating certain embodiments of the invention, aregiven by way of illustration only. From the above discussion and theseExamples, one skilled in the art can ascertain the essentialcharacteristics of this invention, and without departing from the spiritand scope thereof, can make various changes and modifications of theembodiments of the invention to adapt it to various usages andconditions. Thus, various modifications of the embodiments of theinvention, in addition to those shown and described herein, will beapparent to those skilled in the art from the foregoing description.Such modifications are also intended to fall within the scope of theappended claims.

BARDAC 2250 R and 2280 R as used in the Examples herein are availablefrom Lonza, Inc. and are each twin chain dimethyl ammonium chlorides.Bardac 2250 R includes 50 wt % didecyl dimethyl ammonium chloride, 10wt. % ethyl alcohol, and 40 wt. % water. Bardac 2280 R includes 80 wt %didecyl dimethyl ammonium chloride, 10 wt. % ethyl alcohol, and 10 wt. %water. Various other commercially-available quaternary ammoniumcompounds and structures of the raw materials are outlined in Table 2.

TABLE 2 Raw Material Chemical Structure Uniquat QAC-50 Alkyl Benzylammonium chloride Bardac 205M Blend: Dialkyl/Alkyl Benzyl ammoniumchloride Bardac 2250 Didecyl (C10) dimethyl ammonium chloride Bardac2050 Blend: Didecyl/dioctyl dimethyl ammonium chloride Bardac LF80Dioctyl (C8) dimethyl ammonium chloride Acusol 445 4500 MWhomopolyacrylate PSO phosphosuccinate adducts/oligomer AQUATREAT ® lowmolecular weight partially neutralized AR 801 maleic homopolymer Dequest2000 amino tri methylene phosphonic acid scale inhibitor Trilon M methylglycine diacetic acid (MGDA) GLDA glutamic acid-N,N-diacetic acidSurfonic 12-6 decyl/lauryl alcohol ethoxylate with 6 EO

Example 1

Dynamic Surface Tension of Bardac 205M and Anionic Surfactant

The SITA science line t60 measures the dynamic surface tension ofliquids up to the semi-static range. Air bubbles are generated from acapillary with known radius. The bubble pressure is measured as afunction of bubble life time, which can be correlated to the surfacetension according to the Young-Laplace equation. Dynamic surface tensionprovides insight in to the dynamic behavior of surfactants and othersurface active compounds under dynamic conditions, i.e. how quicksurfactants can reach a surface. The dynamic surface tension behavior ofsurfactants is particularly important in applications where a quickresponse of surfactant is required, for example, in short rinse cyclesof automated dishwashing.

Apparatus and Materials

-   1. SITA T60 (Sita Messtechnik, Germany)-   2. Oil bath with stir bar-   3. Heating and stirring plate-   4. Glass beakers-   5. Glass vials (20 mL)

The SITA science line t60 was calibrated with DI water. Clean watersamples after calibration should have a surface tension of 72.0 ±1.0mN/m (depending on the quality and temperature). Following calibration,the SITA was programmed to take readings at the desired time intervals(i.e., 0.3, 1.6, 3.0, 9.1 seconds). In order to determine the effects onthe surface activity of a 9:1 mass ratio of quaternary ammonium compoundwith an anionic surfactant the following compositions were prepared.

Bardac 205M is a commercially available quaternary ammonium compoundfrom Lonza having 20 wt. % active alkyl dimethyl benzyl ammoniumchloride, 15 wt. % octyl decyl dimethyl ammonium chloride, 6 wt. %dioctyl dimethyl ammonium chloride, and 9 wt. % dodecyl dimethylammonium chloride. Bardac 205M quaternary ammonium compound blendfurther includes inert ingredients of 10 wt. % ethyl alcohol and 40 wt.% water. The samples of this Example were prepared using 100 ppmBardac205M. The Bardac 205M was combined each with Plurafac SL-42 (acomparative nonionic surfactant—ethoxylated, propoxylated C6 to C10extended chain surfactant anionic surfactant available from BASF),Surfonic PEA (an amine surfactant—neutral or cationic depending uponpH—comparative ethoxylated ether amine available from HuntsmanChemical), X-AES (anionic surfactant C₁₂₋₁₄—(PO)₁₆-(EO)₂-sulfateavailable from Huntsman Chemical), SLES (anionic surfactant—sodiumlauryl ether sulfate), and Marlowet4539 (C9-alcohol polyethylene glycolether carboxylic acid available from Sasol) at a 9:1 mass ratio.

10-15 mL were transferred into 20 mL vials and immersed in a heated oilbath to 72° C. (160° F.)±2° C. The samples were equilibrated for 10-15minutes. The samples were individually removed from the oil bath andtested in the SITA. After each sample was tested the SITA's cleaningprocedure was run, then the surface tension of DI water was checked toensure the SITA was adequately clean. If the DI water measurements werenot within 72.0±1.0 mN/m, then the cleaning procedure was run again. Thesurface tension (mN/m) versus bubble life time at 160° F. was recordedand the experimental data is provided in FIG. 1.

The results shown in FIG. 1 provide that an increase in dynamic surfaceactivity is observed for most of the quaternary ammonium-anionicsurfactant blends tested. As referred to throughout the Examples, anincrease in dynamic surface activity is shown by a decrease in surfacetension over the course of the bubble lifetime depicted in the figures.Specifically, Bardac 205M +Marlowet4539 and Bardac 205M+Colatrope INCdisplayed a significant increase in surface activity compared to Bardac205M alone. Interestingly, the quat-nonionic surfactant blends, Bardac205M+Plurafac SL-42 and Bardac 205M+Surfonic PEA, displayed only mildsynergy. Whereas, the Bardac 205M with either X-AES or SLES (both ofwhich are longer alkyl alkoxylated sulfates) do not display thesynergistic boost in surface activity observed with the otherquat-anionic surfactant blends.

Example 2

Dynamic Surface Tension of Bardac 205M and Anionic Sulfate SurfactantBlends

To further examine the surface activity of a mole: mole ratio ofquaternary ammonium compound with different anionic sulfate surfactants,the procedure described in Example 1 was followed. Bardac 205M asdescribed above was combined each with SLS (sodium lauryl sulfate), SLES(sodium lauryl ether sulfate), X-AES (C₁₂₋₄—(PO)₁₆-(EO)₂-sulfateavailable from Huntsman Chemical), and Stepanol EH-S (Sodium 2-ETHYLHEXYL SULFATE available from Stepan) at a mole: mole ratio. The resultsare provided in FIG. 2.

The results shown in FIG. 2 demonstrate that the combinations exhibitchain length dependent surface activity as compared to the quaternaryammonium compound (Bardac 205M) alone (at this molar ratio). Forexample, Bardac 205M in combination with EH-S or X-AES or NAS-FAL allshowed a rapid increase in surface activity. Whereas, the Bardac 205M,SLS or SLES blends resulted in an overall increase in surface activitycompared to Bardac 205M alone, but displayed slower dynamics compared tothe other blends tested, illustrating an inactivation of antimicrobialactivity.

Quaternary ammonium compounds themselves are known to have superb microefficacy, however, they are not very surface active material. When thequaternary ammonium compounds are paired with a suitable anionicsurfactant, the combination is more surface active than the twoindividuals. The synergy in antimicrobial efficacy activation correlatesquite well with dynamic surface tension synergy. Without being bound bytheory, we believe that a complex, or ion pair, between a quat andanionic surfactant, because of the charge neutralization, has verysimilar effective cross-sectional areas for both the hydrophile andhydrophobe, making stacking in interfaces very favorable, unless theyare not soluble any more. The complex formation is so favorable that itcan overcome the cohesive force between fatty acid molecules.

Example 3

Dynamic Surface Tension of Mole-Mole Ratio Bardac 205M with AnionicCarboxylate Surfactants

The dynamic surface tension of a mole: mole ratio of quaternary ammoniumcompound with different anionic carboxylate surfactants were testedfollowing the procedure of Example 1. The following solutions wereprepared: Bardac 205M at a concentration of 100 ppm as described abovewas combined each with 48 ppm ethylhexoic acid, 52 ppm Colatrope INC(sodium alkanoate available from Colonial Chemical Inc.), 48 ppmoctanoic acid, 116 ppm Marolwet4539 SLS (C9-alcohol polyethylene glycolether carboxylic acid available from Sasol), 56 ppm decanoic acid, and65 ppm lauric acid at a mole: mole ratio. These data are provided inFIG. 3.

The results shown in FIG. 3A demonstrate that the combinations ofcarboxylated anionic surfactants and quaternary ammonium compounds havereduced surface activity as compared to the quaternary ammonium compound(Bardac 205M) alone. The combination of Bardac 205M with decanoic acidappears to be particularly suitable at increasing the dynamic surfaceactivity compared to Bardac 205M alone. As can be seen in FIG. 3A,ethylhexoic acid, Colatrope INC, octanoic acid, Marolwet4539 SLS,decanoic acid, Lauric acid, and Oleic acid are all capable of increasingthe surface activity, to variable extents, compared to Bardac 205Malone.

Further dynamic surface tension analysis was preformed using the aboveprocedure. The following solutions were prepared: Bardac 205M at aconcentration of 100 ppm as described above was combined with Decanoicacid at varying concentrations (10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm,60 ppm, and 70 ppm) or 100 ppm Decanoate alone. The results are providedin FIG. 3B.

As can be seen by these results, Decanoate alone and Bardac 205M alone,display limited surface activity. However, when each is combined adramatic increase in surface activity is observed. Furthermore, theobserved increase in surface activity of the quat-decanoic acid blendoccurs in a dose-dependent manner. That is, the observed synergistictrend occurs as a function of anionic surfactant concentration.

Beneficially, the medium chain length carboxylated anionic surfactantsshow especially unusual interaction with the quat. In a preferred aspectof the invention, decanoic acid is employed in the antimicrobialcompositions. Decanoic acid is a solid material at room temperature withextremely low solubility yet it dissolves freely with the (slightlyacidic) quat with no addition of any alkalinity. Also, in a wide rangeof pH, the complex formed has very similar strong surface activityproviding an unexpected result. As shown the surface activity isindependent of pH.

Example 4

Dynamic Surface Tension of Bardac 205M and Anionic Sulfate SurfactantCombinations

The surface tension of a mole: mole ratio of quaternary ammoniumcompound with different sulfate based anionic surfactants were examinedfollowing the procedure outlined in Example 1. The following solutionswere prepared. Bardac 205M at a concentration of 100 ppm as describedabove was combined each with 84 ppm SLS (sodium lauryl sulfate), NAS-FAL(sodium n-octanesulfonate), and Stepanol EH-S (Sodium 2-ethyl hexylsulfate available from Stepan) at a mole:mole ratio. These data areprovided in FIGS. 4A, 4B, and 4C respectively.

The results shown in FIG. 4A demonstrate that the mole: mole combinationof sodium lauryl sulfate with quaternary ammonium Bardac 205M displays areduced dynamic surface tension, as compared to either the quaternaryammonium compound or the anionic surfactant alone. Interestingly, whenviewed in combination with the results of FIG. 4B and FIG. 4C, the blendof Bardac 205M+SLS shows a slower decrease in surface tension over thefirst half of the bubble lifetime and then rapid decrease in surfacetension over the second half of the experiment.

The results shown in FIG. 4B are consistent with the results of FIG. 4A.and demonstrate that the mole:mole combination of sodiumn-octanesulfonate with quaternary ammonium Bardac 205M shows asynergistic trend in regards to reduced surface tension as compared toeither the quaternary ammonium compound or the anionic surfactant alone.In contrast to the results of FIG. 4A, a rapid decrease in surfacetension is observed.

The results shown in FIG. 4C are consistent with the observations seenin FIGS. 4A and 4B. As can be seen in FIG. 4C the mole:mole combinationof sodium 2-ethyl hexyl sulfate with quaternary ammonium Bardac 205Malso displays a synergistic reduction of surface tension as compared toeither the quaternary ammonium compound or the anionic surfactant alone.Furthermore, the dynamic decrease in surface tension observed in FIG. 4Cis similar to the dynamics shown in FIG. 4B.

Example 5

Quaternary Ammonium Anionic Surfactant Compound pH Study

In order to determine the effects of pH on the observed synergisticboost in surface activity between the mole: mole ratio of quaternaryammonium compound and carboxylate based anionic surfactant the procedureoutlined in Example 1 was used except the solutions were prepared atvarious pH. Bardac 205M quaternary ammonium was combined with Marlowet4539 (C9-alcohol polyethylene glycol ether carboxylic acid availablefrom Sasol) on a mole: mole basis. The pH of the combination wasadjusted using HCl and the surface tension of the combination at pH 4.0,6.0, 9.0, and 9.5 and plotted for comparison against 100 ppm Bardac 205Mand 116 ppm Marlowet 4539. The results are provided in FIG. 5A.

The data demonstrates the observed synergy between Bardac 205M andMarlowet 4539 is maintained at various pH. The surface tension of thesolutions of Bardac 205M in combination with Marlowet 4539 decrease atcomparable rates regardless of pH. Whereas pH does appear to influencethe surface tension of Marlowet 4539 solutions alone, as the solutionwith a pH of 4.5 was more surface active compared to the solution at apH of 10.0.

Further examination on the effect of pH on the dynamic surface tensionof a combination of mole: mole ratio of 100 ppm Bardac 205M quaternaryammonium compound and 56 ppm decanoic acid were examined as describedabove. The pH of the combination was adjusted and the dynamic surfacetension of the combination was observed at pH 3.6, 4.94, 6, 7, 7.75, 9,and 10.2. The results are provided in FIG. 5B showing the dynamicsurface tension of the mole: mole combination of quaternary ammonium anddecanoic acid was independent of pH. Thus, the dynamic surface tensiondid not vary even though the pH changed. An observation consistent withthe data shown in FIG. 5A.

Example 6

Antimicrobial Efficacy of Quaternary-Anionic Surfactant Compositions

The antimicrobial efficacy of a quaternary ammonium compound inassociation with an anionic surfactant is shown in FIG. 6A utilizing anantimicrobial suspension test. The combinations include a 7.5 to 1 massratio of 300 ppm active Bardac 205M combined with each of SLS, SLES,X-AES, NAS-FAL, Ethylhexyl-Sulfate (EH-S), Colatrope INC, and M4539. Thesame anionic surfactants were combined with 300 ppm Bardac 205M in amole to mole ratio. Bardac 205M is commercially available from Lonzahaving 20 wt. % active alkyl dimethyl benzyl ammonium chloride, 15 wt. %octyl decyl dimethyl ammonium chloride, 6 wt. % dioctyl dimethylammonium chloride, and 9 wt. % dodecyl dimethyl ammonium chloride.Bardac 205M quaternary ammonium compound blend further includes inertingredients of 10 wt. % ethyl alcohol and 40 wt. % water.

The results shown in FIG. 6A demonstrate that the 7.5/1 mass ratio ofBardac 205M to SLS, SLES, X-AES, EH-S and M4539 provided the highest logreduction of bacteria for E. coli. The combined Bardac 205M with SLS,SLES and X-AES also provided good antimicrobial efficacy againstStaphylococcus. Additionally, the data analyzing the mole: mole ratio ofBardac 205M provide the Cola INC and M4539 combinations display thehighest log reduction for E. Coli. The combination of Bardac 205M withNAS-FAL, EH-S, Colatrope INC and M4539 also provided good antimicrobialefficacy against Staphylococcus. While quaternary ammonium compositionsalone are known to be very good antimicrobial agents, however quaternaryammonium compounds are not very surface active compositions limitingtheir usefulness as surface active agents, such as sanitizing agents.These results show that the antimicrobial efficacy is maintained inquaternary ammonium-anionic surfactant compositions, while the surfaceactivity of the combinations are greatly enhanced compared to quaternaryammonium compounds alone (see FIGS. 1-4C).

Further examination of the antimicrobial efficacy of a quaternaryammonium compound in association with an anionic surfactant at pH 8.0was performed as described above. The combinations include a 7.5 to 1mass ratio of 300 ppm, 150 ppm, and 75 ppm active Bardac 205M combinedwith each of SLS, SLES, X-AES, NAS-FAL, Ethylhexyl-Sulfate (EH-S),2-Ethylhexanote, Colatrope INC, Octanoate, Marlowet4539, and Decanoate.Bardac 205M is commercially available from Lonza which composition is asdescribed above. The results are provided in FIG. 6B.

The results demonstrate that the 7.5/1 mass ratio of Bardac 205M to SLS,SLES, X-AES, NAS-FAL, Ethylhexyl-Sulfate, 2-Ethylhexanote, ColatropeINC, Octanoate, Marlowet4539, and Decanoate provided the highest logreduction of bacteria at 300 ppm of the quaternary ammonium compound.The combined Bardac 205M with SLES and X-AES, 2-Ethylhexanoate,Colatrope INC, Octanoate, Marlowet4539, and Decanoate also provided goodantimicrobial efficacy at 150 ppm quaternary ammonium compound.

Example 7

Antimicrobial Efficacy of Quaternary-Anionic Surfactant Compositions

The antimicrobial efficacy of compositions of the invention against E.coli is shown in FIG. 7. Compositions were tested with combinations of300 ppm Bardac quaternary ammonium compound combined in a mole: moleratio with each of SLS, SLES, X-AES, NAS-FAL, Ethylhexyl-Sulfate (EH-S),2-Ethylhexanoate, Colatrope INC, Octanoate, Marlowet4539, and Decanoate.All test compositions were at pH 8.

The results illustrated in FIG. 8 demonstrate that the highest logreduction of bacteria occurred with the combination of Bardac 205M with2-Ethylhexanoate, Colatrope INC and Octanoate. The combination of Bardac205M quaternary ammonium and Marlowet4539 demonstrated bacterial kill toa lesser extent than the others.

The results further demonstrate that rather than heightening theantimicrobial efficacy, some interactions serve to decrease theantimicrobial efficacy of the quaternary ammonium. In particular, withrespect to kill of E. coli, the quaternary ammonium combined each withSLS, SLES, X-AES, NSA-FAL, Ethylhexyl-Sulfate and decanoate all serve toreduce the antimicrobial activity of the quaternary ammonium compound.The interactions between these anionic surfactants and quaternaryammonium compound is said to be destructive or demonstrate a‘deactivation’ effect.

Without being bound by theory, the present invention demonstrates that acomplex, or ion pair, between a quat and anionic surfactant, because ofthe charge neutralization, has very similar effective cross-sectionalareas for both the hydrophile and hydrophobe, making stacking ininterfaces very favorable, unless they are not soluble any more. Thecomplex formation is so favorable that it can overcome the cohesiveforce between fatty acid molecules. This testing demonstrates thestronger ionic bonding as found in sulfates or sulfonates anionicsurfactants work to neutralize, reduce solubility, and/or inactivate anantimicrobial quaternary ammonium compound. It is also believed that dueto weaker ionic bonding, carboxylated anionic surfactants appear toenhance or activate an antimicrobial quaternary ammonium compound. It islikely that other weak acid anionic surfactants such as phosphate esterswould also serve to activate antimicrobial activity.

Example 8

Antimicrobial Efficacy of Quaternary-Anionic Surfactant Compositions

The antimicrobial efficacy on Staphylococcus of a quaternary ammoniumcompound in association with an anionic surfactant at pH 8 is shown inFIG. 8. The combinations include a 7.5 to 1 mass ratio of 300 ppm, 150ppm, and 75 ppm active Bardac 205M combined with each of X-AES,Ethylhexyl-Sulfate (EH-S), 2-Ethylhexanote, Colatrope INC, Octanoate,Marlowet4539, and Decanoate.

The results shown in FIG. 8 demonstrate that the 7.5:1 mass ratio ofBardac 205M to X-AES, Ethylhexyl-Sulfate (EH-S), 2-Ethylhexanote,Colatrope INC, Octanoate, Marlowet4539, and Decanoate at pH 8 alldemonstrated excellent kill properties on Staphylococcus no matter theconcentration of the quaternary ammonium compound. As noted above,sanitizing quaternary ammonium compounds are not very surface activethemselves. The exemplary composition of the present invention, suggeststhe complexes of quat-anioinc surfactant become radically more surfaceactive, while maintaining antimicrobial efficacy.

Example 9

Solubility of Quaternary Ammonium Anionic Surfactant Compositions

Compositions of the invention were prepared using a 1 wt. % Bardac 205Msolution and a mole:mole ratio of a sulfate-based anionic surfactants ora carboxylate-based anionic surfactant according to the table below andobserved appearance behavior in a specimen cup (e.g. precipitation).Each of the resulting combination was observed to determine if a singlephase resulted, whether or not the composition was clear or cloudy, andif precipitation occurred. Results are provided in the Table 3.

TABLE 3 Precipitation/ Type of Anionic Anionic Type of SurfactantSurfactant Phase precipitate Appearance Sulfate-based 0.84 wt % SLSSeparated by Solid precipitate Very cloudy precipitation Sulfate-based0.63 wt % NAS- Separated by Flocculated Clear FAL precipitationprecipitate Sulfate-based 1.2 wt. % SLES Biphasic None Clear with oilphase on top Sulfate-based 0.68 wt % EH- Single None Cloudy sulfateSulfate-based 3.8 wt. % X- Biphasic None Clear with oil AES phase on topCarboxylate- 0.5 wt % Single None Slightly cloudy based ethylhexoic acidCarboxylate- 1.2 wt % Biphasic None Clear with oil based Marlowet4539phase on top Carboxylate- 0.5 wt % Biphasic None Clear with oil basedColatrope INC phase on top Carboxylate- 0.56 wt. % Single None Cloudybased decanoic acid Carboxylate- 0.5 wt % Single None Cloudy basedoctanoic acid Carboxylate- 0.65 wt % lauric Single Solid Cloudy basedacid

Example 10

Antimicrobial Efficacy—Suspension Test

The antimicrobial efficacy of Bardac 205M-Decanoic acid blend againstStaphylococcus was assessed using the food contact sanitizer test methodat pH 4.0 or pH 8.0 and under the outlined conditions in the tables4A-4B. The following solutions were examined: 50 ppm Bardac 205M, 50 ppmBardac 205M+28 ppm Decanoic acid, 75 ppm Bardac 205M, and 75 ppm Bardac205M+42 ppm Decanoic acid. The results are provided in Table 4C and FIG.9A.

TABLE 4A Test Method: MS009: Food Contact Sanitizer Test Organisms: E.coli ATCC 11229 Test Substance Diluent: RTU solutions Exposure Time: 30s Exposure Temp: 25 C. Neutralizer: 9 ml DE Broth Subculture Medium: TGEAgar

TABLE 4B Test Systems: Pseudomonas aeruginosa ATCC 15442 (0.206 A @ 620nm) Test Substance EN Synthetic Hard Water (approx. 375 ppm hardness),Diluent: pH 6.95 Interfering EN Clean Soil Conditions Substances:Exposure Time(s): 5 minutes Neutralizer: 8 mL Chambers Broth + 1 mLsterile water Test Temperature: 20° C. Plating Medium: EN TSAIncubation: 35° C. for 48 hours

TABLE 4C Log Organism Dilution Dilution Dilution Dilution Average AvgInoculum 10e−6 10e−6 10e−7 10e−7 Inoculum Inoc- Numbers Plate 1 Plate 2Plate 1 Plate 2 (CFU/mL) ulum Escherichia 36 63 22 2 5.6E+07 7.75 coliATCC 11229 Staphylococcus 71 63 15 7 7.1E+07 7.85 aureus ATCC 6538Salmonella 46 45 14 9 5.2E+07 7.71 enterica ATCC 10708

Another test was preformed using the procedure described above todetermine the antimicrobial efficacy of Bardac 205M-Decanoci acid blendagainst E. coli. The following solutions were examined: 50 ppm Bardac205M, 50 ppm Bardac 205M+28 ppm Decanoic acid, 75 ppm Bardac 205M, and75 ppm Bardac 205M+42 ppm Decanoic acid. The results are provided inFIG. 9B.

Quaternary ammonium compounds are known to have reduced efficacy in hardwater compared to low water hardness conditions (DI, 5 gpg, 17 gpg).Quat/anionic synergy reduces quaternary ammonium concentrationrequirements for full EPA efficacy and under slightly acidic media (pH˜5and below). Without the presence of water hardness, quat/anionic synergyworking at universal pH and at low concentration of quat (sub 50 ppm).

Example 11

Antimicrobial Efficacy-Hard Water

The antimicrobial efficacy of quaternary ammonium compounds and anionicsurfactants against S. aureus and E. coli were evaluated as shown inTable 5A. A water control, 1% Bardac Quat control and 1% Formula #1provided in Table 5B were examined at pH 7.0.

TABLE 5A Organism Inoculum Numbers Staphylococcus aureus ATCC 6538Escherichia coli ATCC 11229

TABLE 5B Formula #1 wt % Bardac Quat 13.75 Decanoic Acid 2.5 Citric Acid30 Water 53.75The results are provided in the Tables 6-7 below.

TABLE 6 Concentration Water Quat, ppm Contact S. aureus E. coli S.aureus E. coli Hardness, Quat Formula Time, Survivors Survivors Log LogSample Formula ppm Temp pH Control #1 sec. (CFU/mL) (CFU/mL) ReductionReduction 1 Water 250 120 F. 7 0 0 30 304e5 468e5 0.30 0.14 Control 2 1%Quat 250 120 F. 7 75 30  6e3 214e5 3.96 0.48 Control 3 1% Quat 250 120F. 7 100 30 175e1  40e5 4.50 1.20 Control 4 1% 250 120 F. 7 75 30 345e3252e5 2.20 0.40 Formula #1 5 1% 250 120 F. 7 100 30 329e1 131e5 4.220.69 Formula #1

TABLE 7 Concentration Water Quat, ppm Contact S. aureus E. coli S.aureus E. coli Hardness, Quat Formula Time, Survivors Survivors Log LogSample Formula ppm Temp pH Control #1 sec. (CFU/mL) (CFU/mL) ReductionReduction 1 Water 500 120 F. 7 0 0 30 384e5  320e5 0.16 0.30 Control 21% 500 120 F. 7 75 30 101e3  368e5 2.74 0.24 Quat Control 3 1% 500 120F. 7 100 30 13e3 111e5 3.63 0.76 Quat Control 4 1% 500 120 F. 7 75 3055e3 404e5 3.00 0.20 Formula #1 5 1% 500 120 F. 7 100 30 51e3 220e5 3.030.46 Formula #1

The results shown in the above Tables 6-7 confirm that when themicrobes, especially E. coli, are in suspension, they are difficult forquat or quat/anionic blends to kill under hard water, and neutral pHconditions.

An additional test was preformed using the procedure from above, exceptthe pH of the solutions were prepared at pH 7.0 or pH 4.5. The resultsare provided in Tables 8-9.

TABLE 8 Concentration, ppm Water Builder E. coli E. coli Hardness,Citric Contact Survivors Log Sample Formula ppm pH Temp Quat GLDA AcidTime, sec (CFU/mL) Reduction 7 Bardac 500 7.0 120 F. 100 30 130e3 2.71LF80 8 Bardac 500 4.5 120 F. 100 30  50e1 5.15 LF80 9 Sanitizing 500 7.0120 F. 100 50 30 243e3 0.46 Formula #1 10 Sanitizing 500 4.5 120 F. 10050 30  1e1 >6.85 Formula #1 11 Sanitizing 500 7.0 120 F. 100 50 30 154e32.66 Formula #1 12 Sanitizing 500 4.5 120 F. 100 50 30  <1e1 >6.85Formula #1

TABLE 9 Concentration, E. coli E. coli Water ppm Contact SurvivorsSurvivors Hardness, Decanoic Time, (CFU/mL) (CFU/mL) E. coli Log SampleFormula ppm pH Temp Quat Acid sec Rep 1 Rep 2 Reduction 7 Bardac 500 4.5120 F. 100 30 375e1 164e1 4.27 LF80 8 Bardac 500 4.5 120 F. 75 30  47e5 56e5 0.99 LF80 9 Bardac 500 4.5 120 F. 50 30 272e5 200e5 0.33 LF80 10Sanitizing 500 4.5 120 F. 100 25 30  1e1  1e1 >6.41 Formula #1 11Sanitizing 500 4.5 120 F. 75 18.75 30  1e1  1e1 >6.41 Formula #1 12Sanitizing 500 4.5 120 F. 50 12.5 30 264e1  26e3 3.54 Formula #1

The results shown in Tables 8-9 show that the water hardness issue insuspension test is overcome by bringing the pH slightly acidic (pH about4.5). The lower pH helps the quat/decanoic more than the quat alone.Even with 500 ppm water hardness, the efficacy of the quat/decanoic isradically improved at pH 4.5 compared to pH 7.0, demonstrating asynergistic quat/decanoic provides complete kill at 75 ppm quat levelcompared with less than 5 log kill (fail to sanitize) for 100 ppm quatalone.

Example 12

Third Sink Sanitizer

The antimicrobial efficacy of quaternary ammonium compounds and anionicsurfactants for use as a third sink sanitizer were evaluated as shown inTable 10.

TABLE 10 Experimental 3^(rd) Sink Formula Formula wt % Bardac Quat 7.5Decanoic Acid 0.5 Citric Acid 15 Water 77The results are provided in Table 11 below.

Water Concentration, ppm S. aureus E. coli S. aureus E. coli Hardness,Decanoic Emulsogen Contact Survivors Suriviors Log Log Sample ppm pHQuat Acid CNO time, sec (CFU/mL) (CFU/mL) Reduction Reduction 1 500 7.0200 0 0 30 46e1  1e1 5.06 6.81 60 1e1 1e1 6.72 6.81 2 500 4.5 200 0 0 301e1 1e1 6.72 6.81 60 1e1 1e1 6.72 6.81 3 500 7.0 200 75 0 30 12e1 256e5  5.64 0.40 60 1e1 312e5  6.72 0.31 4 500 4.5 200 75 0 30 1e1 5e16.72 6.11 60 1e1 1e1 6.72 6.81 5 500 7.0 200 0 75 30 1e1 59e1  6.72 5.0460 1e1 1e1 6.72 6.81 6 500 4.5 200 0 75 30 1e1 1e1 6.72 6.81 60 1e1 1e16.72 6.81 7 500 7.0 200 75 75 30 7e1 532e5  5.87 0.08 60 1e1 340e5  6.720.28 8 500 4.5 200 75 75 30 1e1 39e1  6.72 5.22 60 16e1  16e1  5.51 6.81

These results confirm that under 500 ppm water hardness condition,decanoate (anionic form at neutral pH) “deactivates” quat, whiledecanoic acid (protonated form at pH 4.5) “synergizes” the quat.However, alcohol ethoxy carboxylate (Emulsogen CNO) does not deactivatethe quat under neutral pH. Without being bound by theory, we believe atneutral pH, the carboxyl groups on the outer wall of microbes such as E.coli are the main attraction sites for quat (opposite chargeattraction). However, the water hardness cations (Ca⁺⁺ and Mg⁺⁺) areeven more attracted to them, effectively “blocking” the quaternaryammonium compounds. The quat/carboxylic combinations according to theinvention provide still further inactivation since the decanoate can beattracted to the Ca⁺⁺ and Mg⁺⁺ that are attached to the microbe outerwalls, making them more hydrophobic (e.g. similar to soap scum). In anaspect, this further confirms why alcohol ethoxy carboxylates farebetter than decanoate as they are not prone to form lime soaps. However,when pH is lowered to about 4.5, some of the carboxyl groups on theouter wall of the microbes are protonated, opening them to quat, andeven more so to the quat/decanoic which is radically more surfaceactive.

Example 13

Food Contact Sanitizing—Hard Water pH Study

Additional testing was done analyzing the antimicrobial efficacy of theQuat-Anioinc surfactant blend in various pH conditions. The compositionsaccording to the invention (and control without both the quaternaryammonium compound and anionic surfactant) and results are provided inTables 12-13.

TABLE 12 Water Concentration Contact E. coli Hardness, Quat AnionicTime, Survivors E. coli Log Sample Formula ppm pH Temp ppm ppm secCFU/mL Reduction 1 Bardac 500 7.0 77 F. 200 30 <1e1 >6.85 205M 2 Bardac500 7.0 77 F. 200 75 30 28e5 1.40 205M + DA 3 Bardac 500 6.5 77 F. 20075 30 34e5 1.31 205M + DA 4 Bardac 500 6.0 77 F. 200 75 30 36e5 1.29205M + DA 5 Bardac 500 5.5 77 F. 200 75 30 >300e5  NA 205M + DA 6 Bardac500 5.0 77 F. 200 75 30 21e1 5.52 205M + These data pinpoint the pH cutoff at approximately pH of 5.

TABLE 13 E. coli E. coli Water Concentration Contact Survivors SurvivorsE. coli Hardness, Quat Anionic Time, (CFU/mL) (CFU/mL) Log SampleFormula ppm pH Temp ppm ppm sec Rep1 Rep2 Reduction 1 Quat 500 4.3 77F75 30 44e5 3e5 1.33 2080 2 Quat 500 4.6 77F 75 12.5 30 1e1 18e1 5.722080 + DA These data clearly showed the quat/decanoic synergy at acidicpH at lower quat level.

These data clearly showed the quat/decanoic synergy at acidic pH atlower quat level.

Example 14

Hard Surface Sanitizing—Hard Water pH Study

Additional testing was done analyzing the antimicrobial efficacy of theQuat-Anioinc surfactant blend in various pH conditions with hard water.The compositions (and control without both the quaternary ammoniumcompound and anionic surfactant), evaluated conditions and results areprovided in Tables 14-18.

TABLE 14 Inoculum Numbers (CFU/mL) Plate 1 Plate 2 Average Escherichiacoli ATCC 11229 125e6 168e6 1.50E+08

TABLE 15 Sanitizing Formula #1 Material Wt % Bardac LF80 13.75 DecanoicAcid 2.5 Emulsogen CNO 4 Plurafac SLF180 11 HEDP, 60% 2.7 DI Water 66.05

TABLE 16 Sanitizing Formula #2 Material Wt % Bardac LF80 13.75 NAS-FAL3.5 Emulsogen CNO 4 Plurafac SLF180 11 HEDP, 60% 2.7 DI Water 65.05

TABLE 17 Swabs from glasses: CFU/ swab Rinse Rinse (CFU/mL × Log10 Log10Test Test Substance Volume Temp. CFU/mL 5) Growth Reduction 1  50 ppmFormula #1 1.7 gal/ 118-120° F. 107e0  5.4E+02 2.73 3.38 rack <1e0 <5<0.70 >5.41 2 100 pppm Formula #1 <1e0 <5 <0.70 >5.51 <1e0 <5<0.70 >5.51 3  50 ppm Formula #2* 50e2 2.5E+04 4.40 1.92 16e0 8.08E+01 1.90 4.42 4 100 pppm Formula #2 <1e0 <5 <0.70 >5.62 <1e0 <5 <0.70 >5.62Untreated Control Counts 1 25e4 1.3E+06 6.11 NA 2 32e4 1.6E+06 6.20 NA 3NT NT NT NA 4 41e4 2.10E+06  6.32 NA Swab from Uninoculated ControlGlass <1e0 <5 <0.70 NA

TABLE 18 Sampling from the sump: CFU/ sample Rinse Rinse (CFU/mL × Log10Test Test Substance Volume Temp. CFU/mL 5) Growth Escherichia coli ATCC11229 1 50 ppm Formula #1 1.7 gal/ 118-120□F. <1e0 <5 <0.70 rack 2 100ppm Formula #1  <1e0 <5 <0.70 3 50 ppm Formula #2 <1e0 <5 <0.70

As shown in Tables 17-18 the unexpected results show that even at veryhard water condition (15 grains per gallon, or 2565 ppm water hardness)the combination of the quat/anionic compositions, as shown thequat/decanoic, provides 5 log kill of the more challenging E. coli, atas low as 50 ppm di-octyl quat level. This confirms that quat/anionic isvery efficacious vs. microbes that are deposited on hard surfaces, evenunder very hard water condition, and at pH neutral or above. Thesampling from the sump confirms that the microbes are killed, not justremoved from the surfaces.

Example 15

High Foaming Non-Molar Ratio Study

Additional testing was done analyzing non-molar ratios of thecompositions on the present invention. The evaluated compositions,conditions and results are provided in Table 19.

TABLE 19 Water Concentration, ppm Contact E. coli E. coli Hardness,Decanoic NAS- Emulsogen Time, Survivors Log Sample ppm pH Quat Acid FALCNO sec (CFU/mL) reduction 1 500 7 200 0 30 1e1 7.01 15 1e1 7.01 2 5004.5 200 0 30 1e1 7.01 15 1e1 7.01 3 500 7 200 25 30 56e1  5.26 15 39e3 3.42 4 500 4.5 200 25 30 1e1 7.01 15 1e1 7.01 5 500 7 200 10 30 1e1 7.0115 43e1  5.37 6 500 4.5 200 10 30 1e1 7.01 15 1e1 7.01 7 500 7 200 25 3027e1  5.58 15 7e1 6.16 8 500 4.5 200 25 30 7e1 6.16 15 13e1  5.89 9 5007 200 50 30 1e1 7.01 15 22e1  5.67 10 500 4.5 200 50 30 1e1 7.01 15158e1  4.81

These results confirm the molar ratios according to compositions of theinvention, namely that many non-molar quat/anionic combos (more quatthan anionic) pass the 500 ppm water hardness suspension tests at bothneutral and acidic pH. However, the further the compositions are from amolar ratio, the surface activity benefit becomes less and lessdemonstrating the trade-off of pH dependence vs. desired surfaceactivity/wetting.

Example 16

Dynamic Surface Tension of Bardac LF80 and Anionic Polymers

The SITA science line t60 measures the dynamic surface tension ofliquids up to the semi-static range. Air bubbles are generated from acapillary with known radius. The bubble pressure is measured as afunction of bubble life time, which can be correlated to the surfacetension according to the Young-Laplace equation. Dynamic surface tensionprovides insight in to the dynamic behavior of surfactants and othersurface active compounds under dynamic conditions, i.e. how quicksurfactants can reach a surface. The dynamic surface tension behavior ofsurfactants is particularly important in applications where a quickresponse of surfactant is required, for example, in short rinse cyclesof automated dishwashing.

Apparatus and Materials

1. SITA T60 (Sita Messtechnik, Germany)

2. Oil bath with stir bar

3. Heating and stirring plate

4. Glass beakers

5. Glass vials (20 mL)

The SITA science line t60 was calibrated with DI water. Clean watersamples after calibration should have a surface tension of 72.0±1.0 mN/m(depending on the quality and temperature). Following calibration, theSITA was programmed to take readings at the desired time intervals(i.e., 0.3, 1.6, 3.0, 9.1 seconds). In order to determine the effects onthe dynamic surface tension of Bardac LF80 and varying concentrations ofAcusol 445 the following five solutions were analyzed at pH 7.0; 100 ppmBardac LF80; 10 ppm Acusol 445; 100 ppm Bardac LF80+10 ppm Acusol 445;100 ppm Bardac LF80+30 ppm Acusol 445; and 100 ppm Bardac LF80+75 ppmAcusol 445.

10-15 mL were transferred into 20 mL vials and immersed in a heated oilbath to 72° C. (160° F.)±2° C. The samples were equilibrated for 10-15minutes. The samples were individually removed from the oil bath andtested in the SITA. After each sample was tested the SITA's cleaningprocedure was run, then the surface tension of DI water was checked toensure the SITA was adequately clean. If the DI water measurements werenot within 72.0±1.0 mN/m, then the cleaning procedure was run again. Thesurface tension (mN/m) versus bubble life time at 160° F. was recordedand shown in FIG. 10.

The data from these experiments demonstrate Bardac LF80 itself showsslow dynamic surface activity. Likewise, Acusol 445 alone shows verylittle surface activity. However, the combination of Bardac LF80 andAcusol 445 are more dynamically active than either of the individuals.Furthermore, increasing synergy between Bardac LF80 and increasinglevels of Acusol 445 can be seen, but the synergy levels off between 30ppm and 75 ppm of Acusol 445.

Further testing of the dynamic surface activity was preformed to assessthe synergy of other Bardac LF80 and polymer combinations. According tothe procedure outlined above, the surface activity of the following fivesolutions at pH 7.0 were determined; 100 ppm Bardac LF80; 100 ppm BardacLF80+75 ppm PSO; 100 ppm Bardac LF80+75 ppm Acusol 445; and 100 ppmBardac LF80+75 ppm AR-801. These results are provided in FIG. 11.

Consistent with the results provided in FIG. 10, the data in FIG. 11clearly shows synergy between Bardac LF80 and the anionic polymerstested (Acusol 445, PSO, and AR-801). The Quat-Anionic polymer solutionsincreased the dynamic surface activity compared to the Quat solutionalone. All three polymers at the concentrations tested were able toincrease the dynamic surface activity of Bardac LF80 at comparablerates.

In order to determine if the observed boost in surface activity inBardac LF80-Anioninc polymer solutions was dependent on pH the followingsolutions were tested according to the procedure above at pH 11.0; 100ppm Bardac LF80; 10 ppm Acusol 445; 100 ppm Bardac LF80+10 ppm Acusol445; 100 ppm Bardac LF80+75 ppm Acusol 445. The results of thisexperiment are provided in FIG. 123.

As can be seen by this data, a change to pH 11.0 has no observableinfluence on the surface activity of Acusol 445 alone. While, thesurface activity of Bardac LF80 alone appears to be increased at pH 11.0when viewed in combination with the results of FIG. 11. However, synergybetween the anionic polymer and quat is still observed indicating thatthe synergistic increase in surface activity is independent of pH.

Example 17

Dynamic Surface Tension of Quat and Anionic Polymers

Investigation of the dynamic surface tension of Quat-Anionic polymerpairs continued as described in Example 16 at pH 7.0 for the followingsolutions; 100 ppm Bardac 2250; 100 ppm Bardac 2250+75 ppm PSO; 100 ppmBardac 2250+75 ppm Acusol 445; 100 ppm Bardac 2250+75 ppm AR-801. Thedata from this experiment is provided in FIG. 13. The results in FIG. 13show a radical difference for Bardac 2250 when viewed in combinationwith the data from FIG. 10, demonstrating different in surface activitybetween a C10 versus C8 quaternary ammonium compound in combination withthe anionic polymer. While Bardac 2250 appears to be synergized by thesmaller PSO and AR-801, it is clear that it becomes in-activated by thelarger anionic polymer Acusol 445.

To further test the in-activation of Bardac 2250 by Acusol 445 theprocedure from Example 16 was used for the following solutions at pH7.0; 100 ppm Bardac 2250; 10 ppm Acusol 445; 100 ppm Bardac 2250+10 ppmAcusol 445; 100 ppm Bardac 2250+20 ppm Acusol 445; and 100 ppm Bardac2250+50 ppm Acusol 445. The results are provided in FIG. 14. As can beseen from this data Acusol 445 shows a dose-dependent in-activation ofBardac 2250 in regards to dynamic surface activity. As the concentrationof Acusol 445 increases the rate at which the surface tension decreasesfor Bardac 2250 over the bubble lifetime is decreased.

In order to determine if the Acusol 445 mediated in-activation of Bardac2250 dynamic surface tension is dependent on the pH of the solution,further testing according to the procedure outlined in Example 16 wasused except the solutions at a pH 7.0 and pH 11.0 were comparedside-by-side. Specifically, the following three solutions were analyzed;100 ppm Bardac 2250; 100 ppm Bardac 2250+50 ppm Acusol 445 at pH 7.0;and 100 ppm Bardac 2250+50 ppm Acusol 445 at pH 11.0. The results areprovided in FIG. 15. The data demonstrates the in-activation of Bardac2250 by Acusol 445 is maintained at pH 11.0. The surface tension of thesolutions of Bardac 2250 in combination with Acusol 445 decrease atcomparable rates regardless of pH. While the surface tension of Bardac2250 alone decreases quickly over the bubble lifetime.

The dynamic surface tension of Quat-Anionic polymer pairs was furtherevaluated using the procedure described in Example 16 to assess theimpact of a combination of C8-C10 quaternary ammonium compounds has onactivation or in-activation. For these experiments the followingsolutions were prepared at pH 7.0; 100 ppm Bardac 205M; 100 ppm Bardac205M+75 ppm PSO; 100 ppm Bardac 205M+75 ppm Acusol 445; and 100 ppmBardac 205M+75 ppm AR-801 (FIG. 16) or 100 ppm Uniquat QAC50; 100 ppmUniquat QAC50+75 ppm PSO; 100 ppm Uniquat QAC50+75 ppm Acusol 445; and100 ppm Uniquat QAC50+75 ppm AR-801 (FIG. 17). The data examining Bardac205M-Anionic polymer pairs are provided in FIG. 16 and the results ofUniquat QAC50-Anioinc polymer pairs are provided in FIG. 17.

Consistent with the results of FIG. 13, the mixture of Bardac 205M isalso synergized by the smaller anionic polymers, PSO and AR-801. As bothPSO and AR-801 in combination with Bardac 205M display a decrease indynamic surface tension compared to Bardac 205M alone. While the largeranionic polymer, Acusol 445, had an in-activating effect on the dynamicsurface tension of Bardac 205M, albeit mildly in-activating compared toFIG. 13. Moreover, the Uniquat QAC50 solutions followed a similar trend,where the smaller anionic polymers, PSO and AR-801 show synergisticsurface activity. However, the mixture of Acusol 445 and Uniquat QAC50show mildly in-activated surface activity (FIG. 17).

The results of Example 16 and Example 17, when viewed in combination,show that Bardac LF80 (C8) and anionic polymer combinations displaysynergistic surface activity boosting properties independent of pH orpolymer size. Whereas, Bardac 2250, Bardac 205M, and Uniquat QAC50, alsoshow synergistic surface activity boosting effects when mixed with thesmaller anionic polymers (PSO and AR-801) but show antagonistic trends(i.e. in-activation) as a function of polymer concentration and pH whenmixed with the larger anionic polymer, Acusol 445.

Example 18

Dynamic Surface Tension of Quat-Chelant Solutions

Using the SITA science line t60 system and the procedure described inExample 16, combinations of Quat-Anionic chelant solutions wereanalyzed. Specifically, the following solutions were analyzed at pH 7.0;100 ppm Bardac LF80; 100 ppm Bardac LF80+10 ppm HEDP; 100 ppm BardacLF80+20 ppm HEDP; 100 ppm Bardac LF80+50 ppm HEDP; and 100 ppm BardacLF80+75 ppm HEDP. These results are shown in FIG. 18. These resultsindicate an increase in dynamic surface activity of Bardac LF80 incombination with HEDP. The synergistic trend appears to be a function ofchelant concentration, although this is a subtle trend.

Additional Quaternary ammonium compounds were tested in combination withanionic chelants according to the procedure outlined in Example 16. Thefollowing solutions were prepared to be tested; 100 ppm Bardac 2250; 100ppm Bardac 2250+75 ppm Dequest 2000; and 100 ppm Bardac 2250+75 ppmTrilon M (FIG. 19) or 100 ppm Uniquat QAC50; 100 ppm Uniquat QAC50+75ppm Dequest 2000; and 100 ppm Uniquat QAC50+75 ppm Trilon M (FIG. 20).The results from the Bardac 2250-Anionic chelant combinations areprovided in FIG. 19 and results from the Uniquat QAC50-Anionic chelantcombinations are provided in FIG. 20.

The data from this experiment shows synergistic surface activityboosting properties of the quat-anionic chelant solutions. For bothBardac 2250 and Uniquat QAC50, an increase in surface activity wasobserved when combined with Dequest 2000 or Trilon M. While, both of theanionic chelants are capable of decreasing the surface tension of allthree Quaternary ammonium compounds tested (Bardac LF80, Bardac 2250,and Uniquat QAC50), Trilon M consistently produced lower surface tensionover bubble lifetime when compared to the Quat-Dequest 2000combinations.

In order to determine the observed synergy of the quat-anionic chelantcombinations is dependent on the pH of the solution, further testingaccording to the procedure outlined in Example 16 was used except atvarying pH. The following solutions were analyzed; 100 ppm Bardac LF80pH 7.0; 100 ppm Bardac LF80+100 ppm Trilon M pH 3.0; 100 ppm BardacLF80+100 ppm Trilon M pH 9.0; and 100 ppm Bardac LF80+Trilon M pH 11.0.The data from this experiment is shown in FIG. 21. As can be seen forthese results, the synergistic trends between Bardac LF80 and Trilon Mappear to be independent of pH, as the pH of the solution had little tono influence on the dynamic surface activity of the solutions tested.

When the results of the experiments of Example 18 are viewed incombination it can be seen that Quat (Bardac LF80, Bardac 2250, andUniquat QAC50) and anionic chelant (Dequest 2000 and Trilon M) showsynergistic surface activity boosting properties when combined, comparedto Quat solutions alone, as seen in FIG. 18-20. In addition, the Quatand anionic chelant synergistic trends are as a function of chelantconcentration and appear to be independent of pH, as shown in FIG. 18and FIG. 21 respectively.

Example 19

Solubility of Quat Anionic Polymer Solutions

A general solution behavior using 1% quat and 100 ppm polymer wasanalyzed. The results are provided in Table 20.

TABLE 20 Solution stability with Quaternary ammonium and Polymers QuatAcusol 445 Results Bardac 205M 10,000 ppm 100 ppm Cloudy Soln. Bardac2250 10,000 ppm 100 ppm Cloudy Soln. Bardac LF80 10,000 ppm 100 ppmCloudy Soln.

Further solution behavior using 500 ppm quat and the maximum addition ofpolymer before phase change (precipitation point) was analyzed. Thepolymer was added to a maximum concentration (insolubility point). Theresults are provided in Table 21.

TABLE 21 Solution stability with Quaternary ammonium and Polymers QuatAcusol 445 Results Bardac 205M 500 ppm  90 ppm Hazy Bardac 2250 500 ppm160 ppm Hazy Bardac LF80 500 ppm 1500+ ppm  Transparent

The results from these experiments show the shorter chain length on thequaternary ammonium, favored higher levels of polymer incorporation.

Example 20

Mineral Deposit Removal

To determine the efficacy of Quat-anionic chelant and Quat-anionicpolymer combinations to remove soil from the surface of an object thefollowing procedure was used. Using an automated dip tester unit,pre-soiled polypropylene coupons (mineral deposit) were dipped into asolutions of water, 50 ppm Chelant (GLDA), and 100 ppm Bardac LF80+50ppm Chelant (GLDA). The solutions were prepared and stirred in separatebeakers. The soiled tiles were submerged into beakers of the variouscleaning compositions for a period of time 10 minutes. Thereafter thetile was visually analyzed to assess the cleanliness of the tile, namelythe mineral deposit removal. Visual observation of this scale removalfor the Quat-anionic chelant solutions and the Quat-anionic polymersolutions are shown in FIG. 22.

Using the same automated dip tester unit, pre-soiled polypropylenecoupons (mineral deposit) were dipped into a solutions of water, 25 ppmAcusol 445, 100 ppm Bardac LF80+25 ppm Acusol 445, and 100 ppm nonionicsurfactant (Surfonic 12-6)+25 ppm Acusol 445. Visual observation ofscale removal for the Quat-anionic chelant solutions and theQuat-anionic polymer solutions are shown in FIG. 23.

The results show a benefit of using a synergistic combination of thequat and anionic polymer/chelant according to embodiments of theinvention. The combination enhances the soil removal power of thechelants and polymers, more than a non-synergistic nonionic surfactantin combination with the anionic polymer (as shown by 100 ppm nonionicsurfactant (Surfonic 12-6)+25 ppm Acusol 445). Without being bound by aparticular mechanism of action or theory of the invention, the quat andanionic polymer/chelant forms a more surface active complex with thechelating agent or polymer, which effectively seeks out the scales on asurface through surface excess and/or less charge repulsion mechanism.Although the non-synergistic surfactants (i.e. nonionic surfactant) canimprove wetting, no surface excess and/or less charge repulsion of thechelating agent and/or polymer exists.

The inventions being thus described, it will be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the inventions and all suchmodifications are intended to be included within the scope of thefollowing claims. The above specification provides a description of themanufacture and use of the disclosed compositions and methods. Sincemany embodiments can be made without departing from the spirit and scopeof the invention, the invention resides in the claims.

1. An antimicrobial composition, comprising: a quaternary ammoniumcompound having the formula:

wherein groups R1, R2, R3, and R4 each have less than a C20 chainlength, and an anionic surfactant having C6-C18 chain length, anionicpolymer or anionic chelant; wherein the composition is a ready to usesolution, or a solid or liquid concentrate that is soluble in water, hasa pH of about 1 to about 12 and is substantially free of silanes, andoxidants.
 2. The antimicrobial composition of claim 1, wherein theanionic surfactant is an alkoxylated or un-alkoxylated linear orbranched chain carboxylate and/or phosphate ester, and wherein thequaternary ammonium compound is selected from the group consisting ofmonoalkyltrimethyl ammonium salts, monoalkyldimethylbenzyl ammoniumsalts, dialkyldimethyl ammonium salts, heteroaromatic ammonium salts,polysubstituted quaternary ammonium salts, bis-quaternary ammoniumsalts, polymeric quaternary ammonium salts, and combinations thereof. 3.The antimicrobial composition of claim 1, wherein the pH is betweenabout 1 and about 10, the composition optionally includes an acidulant,and wherein the molar ratio of anionic surfactant, chelant or polymer toquaternary ammonium is from about 10 moles anionic surfactant, chelantor polymer to about 1 mole of quaternary ammonium to about 1 moleanionic surfactant, chelant or polymer to about 10 moles of quaternaryammonium.
 4. The antimicrobial composition of claim 1, wherein theanionic surfactant is a primary linear chain carboxylate selected fromthe group consisting of a medium chain surfactant having C6-C10 chainlength and a medium chain surfactant having C8-C10 chain length.
 5. Theantimicrobial composition of claim 1, wherein the anionic chelant orpolymer is an aminocarboxylate or derivative thereof, a phosphonic acidor phosphonate salt.
 6. The antimicrobial composition of claim 1,wherein the molar ratio of anionic surfactant, chelant or polymer toquaternary ammonium is from about 1 mole anionic surfactant, chelant orpolymer to about 1 mole of quaternary ammonium.
 7. The antimicrobialcomposition of claim 1, wherein the quaternary ammonium compound iscomprised of one or more of dialkyl quaternary ammonium and alkyl benzylquaternary ammonium and wherein the anionic surfactant is comprised ofone or more of octanoic acid, nonanoic acid or decanoic acid.
 8. Theantimicrobial composition of claim 1, wherein the quaternary ammoniumhas a carbon chain length of 8 to 20 carbon atoms, and wherein thequaternary ammonium compound groups R1, R2, R3, and R4 each have lessthan a C10 chain length.
 9. The antimicrobial composition of claim 8,wherein the quaternary ammonium compound is a dioctyl (C8) dimethylammonium chloride, didecyl (C10) dimethyl ammonium chloride, dialkylbenzyl ammonium chloride and/or alkyl Benzyl ammonium chloride, andwherein the anionic surfactant, chelant or polymer is a polyacrylic acidpolymer, a phosphosuccinate adduct/oligomer (PSO), and/or apolycarboxylate.
 10. The antimicrobial composition of claim 1, whereinthe composition provides in a use solution from about 50 ppm to about400 ppm quaternary ammonium compound and at least about 10 ppm anionicsurfactant, chelant or polymer.
 11. The antimicrobial composition ofclaim 1, further comprising an additional functional ingredient selectedfrom the group consisting of additional surfactants, thickeners and/orviscosity modifiers, solvents, solubility modifiers, humectants, metalprotecting agents, stabilizing agents, corrosion inhibitors,sequestrants and/or chelating agents, solidifying agent, sheetingagents, pH modifying components (acidulant), fragrances and/or dyes,hydrotropes or couplers, buffers, and combinations thereof.
 12. A methodof killing microbes comprising: applying to a substrate theantimicrobial composition of claim 1; wherein the composition providesat least 5 log kill and/or decreases scale deposits on treated surfaces.13. The method of claim 12, wherein the pH of the composition is betweenabout 1 and about 7, and wherein the use solution conditions have awater hardness of greater than 5 grains per gallon (gpg).
 14. A methodof rapidly solubilizing a fatty acid to enhance antimicrobial efficacycomprising: adding to a fatty acid a quaternary ammonium having theformula:

wherein groups R1, R2, R3, and R4 each have less than a C20 chainlength, wherein the solubilization de-odorizes unpleasant fatty acidsmell.
 15. The method of claim 14, wherein the fatty acid is acarboxylic fatty acid, and wherein the combining of the fatty acid thequaternary ammonium is in water.
 16. The method of claim 14, wherein themolar ratio of carboxylic fatty acid to quaternary ammonium is fromabout 2 moles carboxylic fatty acid to about 1 mole of quaternaryammonium to about 1 mole carboxylic fatty acid to about 10 moles ofquaternary ammonium.
 17. A method for using an anionic surfactant forinactivating an antimicrobial quaternary composition, comprising:treating a water source or waste stream comprising a quaternary ammoniumcompound having the formula:

wherein groups R1, R2, R3, and R4 each have less than a C20 chainlength, with an anionic surfactant having at least a C12 chain lengthand less than a C20 chain length; wherein the anionic surfactant has apH of about 1 to about 12, and wherein water source or waste streamcontains bacteria which are not disrupted by the inactivatedcomposition.
 18. The method of claim 17, wherein the anionic surfactantis (i) a sulfate and/or sulfonate anionic surfactant or a polyacrylicacid polymer having a molecular weight greater than about 4000, (ii) isselected from the group consisting of SLS (sodium lauryl sulfate), SLES(sodium lauryl ether sulfate), LAS (linear alkyl benzyl sulfonate) andAOS (alpha olefin sulfonate), or (iii) a linear chain or branched chain,alkoxylated or unalkoxylated sulfate or sulfonate, and wherein thequaternary ammonium compound is selected from the group consisting ofmonoalkyltrimethyl ammonium salts, monoalkyldimethylbenzyl ammoniumsalts, dialkyldimethyl ammonium salts, heteroaromatic ammonium salts,polysubstituted quaternary ammonium salts, bis-quaternary ammoniumsalts, polymeric quaternary ammonium salts, and combinations thereof.19. The method of claim 17, wherein the inactivated antimicrobialcomposition is effective under hard water conditions.
 20. The method ofclaim 17, wherein the molar ratio of anionic surfactant to quaternaryammonium compound is from about 10 moles anionic surfactant to about 1mole of quaternary ammonium compound to about 1 mole anionic surfactantto about 10 moles of quaternary ammonium, and wherein the molar ratiocontrols the degree of inactivation of the quaternary ammonium compound.21. A kit for inactivating a surface active and/or antimicrobialcomposition comprising a quaternary ammonium compound, comprising: (a)an anionic surfactant having at least a C12 chain length and less than aC20 chain length; and (b) a measuring means and/or dosing means fordetermining and/or providing a molar ratio of the anionic surfactant toa quaternary ammonium compound having the formula:

wherein groups R1, R2, R3, and R4 each have less than a C20 chainlength, wherein the wherein the molar ratio of anionic surfactant toquaternary ammonium compound is from about 1 mole anionic surfactant toabout 1 mole of quaternary ammonium compound.
 22. The kit of claim 21,further comprising instructions.